Herbicidal sulphonylaminoguanidinoazines

ABSTRACT

Herbicidally active sulphonylamino guanidinoazines of the formula ##STR1## in which R 1  stands for an optionally substituted radical from the series comprising alkyl, aralkyl, aryl and hetaryl, 
     R 2  stands for an optionally substituted radical from the series comprising alkyl, aralkyl, aryl, hetaryl and dialkylamino, 
     R 3  stands for hydrogen, halogen, hydroxyl, alkyl, halogenaoalkyl, alkoxyalkyl, alkoxy, halogenoalkoxy, alkylthio, halogenoalkylthio, amino, alkylamino or dialkylamino, 
     R 5  stands for hydrogen, halogen, hydroxyl, alkyl, alkoxy, halogenoalkoxy, alkylthio, alkylamino or dialkylamino, and 
     M stands for hydrogen, a metal equivalent, an ammonium equivalent, an alkylammonium equivalent, a dialkylammonium equivalent, or a trialkylammonium equivalent.

This is a continuation-in-part of application Ser. No. 521,055, filed May 2, 1990, now abandoned (which is a division of Ser. No. 227,587, filed Aug. 2, 1988, now U.S. Pat. No. 4,952,233) and of Ser. No. 561,857, filed Aug. 1, 1990, now U.S. Pat. No. 5,125,960.

The invention relates to new sulphonylaminoguanidinoazines, a process for their preparation and their use as herbicides.

It has already been disclosed that certain aminoguanidinoazines, such as, for example, N'-(4,6-dimethylpyrimidin-2-yl)-N"-acetamido-N"'-(2-chlorophenylsulphonyl)guanidine exhibit herbicidal properties (compare EP-A 121,082).* The herbicidal action of the hitherto known aminoguanidinoazines is not always very satisfactory, however.

New sulphonylaminoguanidinoazines of the general formula (I) ##STR2## in which R¹ stands for an optionally substituted radical from the series comprising alkyl, aralkyl, aryl and hetaryl, R² stands for an optionally substituted radical from the series comprising alkyl, aralkyl, aryl, hetaryl and dialkylamino,

R³ stands for hydrogen, halogen, hydroxyl, alkyl, halogenoalkyl, alkoxyalkyl, alkoxy, halogenoalkoxy, alkylthio, halogenoalkylthio, amino, alkylamino or dialkylamino,

X stands for nitrogen or a --CH-grouping,

Y stands for nitrogen or a --CR⁴ -grouping,

wherein

R⁴ stands for hydrogen, halogen, cyano, alkyl, formyl, alkyl-carbonyl or alkoxy-carbonyl,

Z stands for nitrogen or a --CR⁵ -grouping,

wherein

R⁵ stands for hydrogen, halogen, hydroxyl, alkyl, alkoxy, halogenoalkoxy, alkylthio, alkylamino or dialkylamino, and

M stands for hydrogen, a metal equivalent, an ammonium equivalent, an alkylammonium equivalent, a dialkylammonium equivalent, or a trialkylammonium equivalent,

have now been found, where N'-(4,6-dimethyl-pyrimidin-2-yl)-N"-(4-methyl-phenylsulphonylamino)-N"'-(2-chloro-phenylsulphonyl)-guanidine--known from EP-A 121,082--is excluded.

The general formula (I) stands--when M stands for hydrogen--for the individual possible tautomers of the formulae (IA), (IB) and (IC) ##STR3## and also for mixtures of these tautomers.

The new sulphonylaminoguanidinoazines of the general formula (I) are obtained when sulphonyl compounds of the general formula (II) ##STR4## in which R¹, R³, X, Y and Z have the abovementioned meanings and

A stands for one of the leaving groups ##STR5## wherein R⁶ has the abovementioned meaning for R¹, but does not have to be identical with R¹ in each individual case,

R⁷ stands for alkyl, alkenyl or aralkyl,

R⁸ stands for alkyl, aralkyl or aryl and

Q stands for oxygen or sulphur,

are reacted with sulphonyl hydrazides of the general formula (III)

    R.sup.2 --SO.sub.2 --NH--NH.sub.2                          (III)

in which

R² has the aforementioned meaning,

if desired in the presence of a diluent, and the products thus obtained are converted if desired into salts by customary methods.

The new sulphonylaminoguanidinoazines of the general formula (I) are distinguished by strong herbicidal activity.

Surprisingly, the new compounds of the general formula (I) show a considerably better herbicidal action than previously known aminoguanidinoazines with an equivalent type of action.

The invention preferably relates to compounds of the formula (I) in which

R¹ stands for the radical ##STR6## wherein R⁹ and R¹⁰ are identical of different and stand for hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, C₁ -C₆ -alkyl [which is optionally substituted by fluorine, chlorine, bromine, cyano, carboxyl, C₁ -C₄ -alkoxycarbonyl, C₁ -C₄ -alkylamino-carbonyl, di-(C₁ -C₄ -alkyl)-amino-carbonyl, hydroxyl, C₁ -C₄ -alkoxy, formyloxy, C₁ -C₄ -alkylcarbonyloxy, C₁ -C₄ -alkoxy-carbonyloxy, C₁ -C₄ -alkylamino-carbonyloxy, C₁ -C₄ -alkylthio, C₁ -C₄ -alkylsulphinyl, C₁ -C₄ -alkylsulphonyl, di-(C₁ -C₄ -alkyl)-aminosulphonyl, C₃ -C₆ -cycloalkyl or phenyl], for C₂ -C₆ -alkenyl [which is optionally substituted by fluorine, chlorine, bromine, cyano, C₁ -C₄ -alkoxycarbonyl, carboxyl or phenyl], for C₂ -C₆ -alkinyl [which is optionally substituted by fluorine, chlorine, bromine, cyano, C₁ -C₄ -alkoxy-carbonyl, carboxyl or phenyl], for C₁ -C₄ -alkoxy [which is optionally substituted by fluorine, chlorine, bromine, cyano, carboxyl, C₁ -C₄ -alkoxy-carbonyl, C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio, C₁ -C₄ -alkylsulphinyl or C₁ `C₄ -alkylsulphonyl], for C₁ -C₄ -alkylthio [which is optionally substituted by fluorine, chlorine, bromine, cyano, carboxyl, C₁ -C₄ -alkoxy-carbonyl, C₁ -C₄ -alkylthio, C₁ -C₄ -alkylsulphinyl or C₁ -C₄ -alkylsulphonyl], for C₃ -C₆ -alkenyloxy [which is optionally substituted by fluorine, chlorine, bromine, cyano or C₁ -C₄ -alkoxycarbonyl], for C₂ -C₆ -alkenylthio [which is optionally substituted by fluorine, chlorine, bromine, cyano, nitro, C₁ -C₃ -alkylthio or C₁ -C₄ -alkoxycarbonyl], C₃ -C₆ -alkinyloxy, C₃ -C₆ -alkinylthio or for the radical --S(O)_(p) --R¹¹,

wherein

p stands for the numbers 1 or 2 and

R¹¹ stands for C₁ -C₄ -alkyl [which is optionally substituted by fluorine, chlorine, bromine, cyano or C₁ -C₄ -alkoxy-carbonyl], C₃ -C₆ -alkenyl, C₃ -C₆ -alkinyl, C₁ -C₄ -alkoxy, C₁ -C₄ -alkoxy-C₁ -C₄ -alkylamino, C₁ -C₄ -alkylamino, di-(C₁ -C₄ -alkyl)-amino or for the radical --NHOR¹²,

wherein

R¹² stands for C₁ -C₁₂ -alkyl [which is optionally substituted by fluorine, chlorine, cyano, C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio, C₁ -C₄ -alkylsulphinyl, C₁ -C₄ -alkylsulphonyl, C₁ -C₄ -alkylcarbonyl, C₁ -C₄ -alkoxy-carbonyl, C₁ -C₄ -alkylamino-carbonyl or di-(C₁ -C₄ -alkyl)-amino-carbonyl], for C₃ -C₆ -alkenyl [which is optionally substituted by fluorine, chlorine or bromine], C₃ -C₆ -alkinyl, C₃ -C₆ -cycloalkyl, C₃ -C₆ -cycloalkyl-C₁ -C₂ -alkyl, phenyl-C₁ -C₂ -alkyl [which is optionally substituted by fluorine, chlorine, nitro, cyano, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy or C₁ -C₄ -alkoxycarbonyl], for benzohydryl or for phenyl [which is optionally substituted by fluorine, chlorine, nitro, cyano, C₁ -C₄ -alkyl, trifluoromethyl, C₁ -C₄ -alkoxy, C₁ -C₂ -fluoroalkoxy, C₁ -C₄ -alkylthio, trifluoromethylthio or C₁ -C₄ -alkoxy-carbonyl],

R⁹ and R¹⁰ furthermore stand for phenyl or phenoxy, for amino, C₁ -C₄ -alkylcarbonylamino, C₁ -C₄ -alkoxy-carbonylamino, C₁ -C₄ -alkylamino-carbonylamino, di-(C₁ -C₄ -alkyl)-amino-carbonylamino, or for the radical --CO--R¹³,

wherein

R¹³ stands for C₁ -C₆ -alkyl, C₁ -C₆ -alkoxy, C₃ -C₆ -cycloalkoxy, C₃ -C₆ -alkenyloxy, C₁ -C₄ -alkylthio, C₁ -C₄ -alkylamino, C₁ -C₄ -alkoxyamino, C₁ -C₄ -alkoxy-C₁ -C₄ -alkyl-amino or di-(C₁ -C₄ -alkyl)-amino [which are optionally substituted by fluorine and/or chlorine],

R⁹ and R¹⁰ furthermore stand for C₁ -C₄ -alkylsulphonyloxy, di-(C₁ -C₄ -alkyl)-aminosulphonylamino, thiazolyloxy or for the radical --CH═N--R¹⁴,

wherein

R¹⁴ stands for C₁ -C₆ -alkyl which is optionally substituted by fluorine, chlorine, cyano, carboxyl, C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio, C₁ -C₄ -alkylsulphinyl or C₁ -C₄ -alkylsulphonyl, for benzyl which is optionally substituted by fluorine or chlorine, for C₃ -C₆ -alkenyl or C₃ -C₆ -alkinyl which are optionally substituted by fluorine or chlorine, for phenyl which is optionally substituted by fluorine, chlorine, bromine, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, trifluoromethyl, trifluoromethoxy or trifluoromethylthio, for C₁ -C₆ -alkoxy, C₃ -C₆ -alkenoxy, C₃ -C₆ -alkinoxy or benzyloxy which are optionally substituted by fluorine and/or chlorine, for amino, C₁ -C₄ -alkylamino, di-(C₁ -C₄ -alkyl)-amino, phenylamino, C₁ -C₄ -alkyl-carbonyl-amino, C₁ -C₄ -alkoxy-carbonylamino, C₁ -C₄ -alkyl-sulphonylamino or for phenylsulphonylamino which is optionally substituted by fluorine, chlorine, bromine or methyl,

wherein in addition,

R¹ stands for the radical ##STR7## wherein R¹⁵ stands for hydrogen or C₁ -C₄ -alkyl,

R¹⁶ and R¹⁷ are identical or different and stand for hydrogen, fluorine, chlorine, bromine, nitro, cyano, C₁ -C₄ -alkyl [which is optionally substituted by fluorine and/or chlorine], C₁ -C₄ -alkoxy [which is optionally substituted by fluorine and/or chlorine], carboxyl, C₁ -C₄ -alkoxy-carbonyl, C₁ -C₄ -alkylsulphonyl or di-(C₁ -C₄ -alkyl)-aminosulphonyl;

wherein in addition

R¹ stands for the radical ##STR8## wherein R¹⁸ and R¹⁹ are identical or different and stand for hydrogen, fluorine, chlorine, bromine, nitro, cyano, C₁ -C₄ -alkyl [which is optionally substituted by fluorine and/or chlorine] or C₁ -C₄ -alkoxy [which is optionally substituted by fluorine and/or chlorine];

wherein in addition

R¹ stands for the radical ##STR9## wherein R²⁰ and R²¹ are identical or different and stand for hydrogen, fluorine, chlorine, bromine, nitro, cyano, C₁ -C₄ -alkyl [which is optionally substituted by fluorine and/or chlorine], C₁ -C₄ -alkoxy [which is optionally substituted by fluorine and/or chlorine], for C₁ -C₄ -alkylthio, C₁ -C₄ -alkylsulphinyl or C₁ -C₄ -alkylsulphonyl [which are optionally substituted by fluorine and/or chlorine], and also for di-(C₁ -C₄ -alkyl)-aminosulphonyl or C₁ -C₄ -alkoxy-carbonyl;

wherein in addition

R¹ stands for the radical ##STR10## wherein R²² and R²³ are identical or different and stand for hydrogen, fluorine, chlorine, bromine, C₁ -C₄ -alkyl [which is optionally substituted by fluorine and/or bromine], C₁ -C₄ -alkoxy [which is optionally substituted by fluorine and/or chlorine], for C₁ -C₄ -alkylthio, C₁ -C₄ -alkylsulphinyl or C₁ -C₄ -alkylsulphonyl [which are optionally substituted by fluorine and/or chlorine], or for di-(C₁ -C₄ -alkyl)-aminosulphonyl;

wherein in addition

R¹ stands for the radical ##STR11## wherein R²⁴ and R²⁵ are identical or different and stand for hydrogen, fluorine, chlorine, bromine, cyano, nitro, C₁ -C₄ -alkyl [which is optionally substituted by fluorine and/or chlorine], C₁ -C₄ -alkoxy [which is optionally substituted by fluorine and/or chlorine], C₁ -C₄ -alkylthio, C₁ -C₄ -alkylsulphinyl or C₁ -C₄ -alkylsulphonyl [which is optionally substituted by fluorine and/or chlorine], di-(C₁ -C₄ -alkyl)-amino-sulphonyl or C₁ -C₄ -alkoxy-carbonyl, and

A stands for oxygen, sulphur or the grouping N--Z¹,

wherein

Z¹ stands for hydrogen, C₁ -C₄ -alkyl [which is optionally substituted by fluorine, chlorine, bromine or cyano], C₃ -C₆ -cycloalkyl, benzyl, phenyl [which is optionally substituted by fluorine, chlorine, bromine or nitro], C₁ -C₄ -alkylcarbonyl, C₁ -C₄ -alkoxy-carbonyl or di-(C₁ -C₄ -alkyl)-aminocarbonyl;

wherein in addition

R¹ stands for the radical ##STR12## wherein R²⁶ stands for hydrogen, C₁ -C₅ -alkyl or halogen,

R²⁷ stands for hydrogen or C₁ -C₅ -alkyl and

Y¹ stands for sulphur or the grouping N--R²⁸,

wherein

R²⁸ stands for hydrogen or C₁ -C₅ -alkyl,

wherein in addition

R¹ stands for the radical ##STR13## wherein R²⁹ stands for hydrogen, C₁ -C₄ -alkyl or phenyl,

R³⁰ stands for hydrogen, halogen, cyano, nitro, C₁ -C₄ -alkyl [which is optionally substituted by fluorine and/or chlorine], C₁ -C₄ -alkoxy [which is optionally substituted by fluorine and/or chlorine] or C₁ -C₄ -alkoxy-carbonyl and

R³¹ stands for hydrogen, halogen or C₁ -C₄ -alkyl,

wherein in addition,

R¹ stands for the radical ##STR14## wherein R³² stands for C₁ -C₃ -alkyl and

R³³ stands for C₁ -C₄ -alkyl,

wherein in addition

R¹ stands for the radical ##STR15## in which in addition R² has the meaning given above as preferred for R¹, but does not have to be identical with R¹ in each individual case, and in addition can stand for di-(C₁ -C₃ -alkyl)-amino or for C₁ -C₈ -alkyl which is optionally substituted by halogen,

in which in addition

R³ stands for hydrogen, fluorine, chlorine, bromine, C₁ -C₄ -alkyl, C₁ -C₄ -halogenoalkyl, C₁ -C₂ -alkoxy-C₁ -C₂ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -halogenoalkoxy, C₁ -C₄ -alkylthio, C₁ -C₄ -halogenoalkylthio, amino, C₁ -C₄ -alkylamino, dimethylamino or diethylamino,

X stands for nitrogen or a --CH-- grouping,

Y stands for nitrogen or a --CR⁴ -- grouping,

wherein

R⁴ stands for hydrogen, fluorine, chlorine, bromine, cyano, methyl, formyl, acetyl, methoxycarbonyl or ethoxycarbonyl and

Z stands for nitrogen or a --CR⁵ -- grouping,

wherein

R⁵ stands for hydrogen, fluorine, chlorine, bromine, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -halogenoalkoxy, C₁ -C₄ -alkylthio, C₁ -C₄ -alkylamino, dimethylamino or diethylamino, and

M stands for hydrogen or a sodium equivalent, a potassium equivalent or a calcium equivalent, an ammonium equivalent, a C₁ -C₆ -alkylammonium equivalent, a di-(C₁ -C₄ -alkyl)-ammonium or a tri-(C₁ -C₄ -alkyl)-ammonium equivalent,

where

N'-(4,6-dimethyl-pyrimidin-2-yl)-N"-(4-methylphenylsulphonylamino)-N"'-(2-chloro-phenylsulphonyl)-guanidine is excluded.

The invention relates in particular to compounds of the formula (I)

in which

R¹ stands for the radical ##STR16## wherein R⁹ stands for fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy, difluoromethoxy, trifluoromethoxy, C₁ -C₃ -alkylthio, C₁ -C₃ -alkylsulphinyl, C₁ -C₃ -alkylsulphonyl, dimethylaminosulphonyl, diethylaminosulphonyl, N-methoxy-N-methylaminosulphonyl, phenyl, phenoxy or C₁ -C₃ -alkoxycarbonyl and

R¹⁰ stands for hydrogen;

wherein in addition

R¹ stands for the radical ##STR17## wherein R¹⁵ stands for hydrogen,

R¹⁶ stands for fluorine, chlorine, bromine, methyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, methoxycarbonyl, ethoxycarbonyl, methylsulphonyl or dimethylaminosulphonyl and

R¹⁷ stands for hydrogen;

wherein in addition

R¹ stands for the radical ##STR18## wherein R stands for C₁ -C₂ -alkyl, or

R¹ stands for the radical ##STR19## wherein R stands for C₁ -C₂ -alkyl;

in which in addition

R² stands for C₁ -C₄ -alkyl which is optionally substituted by fluorine or chlorine or for phenyl which is optionally substituted by fluorine, chlorine, bromine, C₁ -C₃ -alkyl, trifluoromethyl, chlorodifluoromethyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, amino, acetamido, methoxycarbonyl and/or ethoxycarbonyl,

R³ stands for hydrogen, fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, methylthio, ethylthio, amino, methylamino, ethylamino, dimethylamino or diethylamino,

X stands for nitrogen or a --CH-- grouping,

Y stands for nitrogen or a --CR⁴ -- grouping,

wherein

R⁴ stands for hydrogen, fluorine, chlorine or methyl,

Z stands for nitrogen or a --CR⁵ -- grouping,

wherein

R⁵ stands for hydrogen, fluorine, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, propoxy, isopropoxy, difluoromethoxy, methylthio, ethylthio, methylamino, ethylamino, dimethylamino or diethylamino, and

M stands for hydrogen or a sodium equivalent, potassium equivalent or calcium equivalent, an ammonium equivalent or a C₁ -C₄ -alkyl-ammonium equivalent, where N'-(4,6-dimethyl-pyrimidin-2-yl)-N"-(4-methylphenylsulphonylamino)-N"'-(2-chloro-phenylsulphonyl)-guanidine is excluded.

If, for example, N'-(4,6-dimethoxy-s-triazin-2-yl)-N"-methoxy-N",N"'-bis-(2-bromo-phenylsulphonyl)-guanidine and trifluoromethanesulphonyl hydrazide are used as starting materials, then the course of the reaction in the process according to the invention can be represented by the following equation: ##STR20##

Formula (II) provides a general definition of the sulphonyl compounds to be used as starting materials in the process according to the invention. In the formula (II), R¹, R³, X, Y and Z preferably or particularly have those meanings which have already been given above as preferred or particularly preferred for R¹, R³, X, Y and Z in the scope of the description of the compounds of the formula (I) according to the invention and

A preferably stands for one of the leaving groups ##STR21## wherein R⁶ has the meaning given above as preferred for R¹, but need not be identical with R¹ in each individual case,

R⁷ stands for C₁ -C₄ -alkyl, C₃ -C₄ -alkenyl or benzyl,

R⁸ stands for C₁ -C₄ -alkyl, benzyl or phenyl and

Q stands for oxygen or sulphur.

In particular, A stands for the grouping ##STR22## wherein R⁶ has the meaning given above as particularly preferred for R¹, but does not have to be identical with R¹ in each individual case and

R⁷ stands for methyl.

Examples of the starting materials of the formula (II) are shown in Table 1 below.

                                      TABLE 1                                      __________________________________________________________________________     Examples of starting materials of the formula (II)                              ##STR23##                                       (II)                          A                  R.sup.1         R.sup.3                                                                             X Y  Z                                 __________________________________________________________________________      ##STR24##                                                                                         ##STR25##      CH.sub.3                                                                            N CH COCH.sub.3                         ##STR26##                                                                                         ##STR27##      OCH.sub.3                                                                           N CH COCH.sub.3                         ##STR28##                                                                                         ##STR29##      OCH.sub.3                                                                           N CH COCH.sub.3                         ##STR30##                                                                                         ##STR31##      OCH.sub.3                                                                           N CH COCH.sub.3                         ##STR32##                                                                                         ##STR33##      OCH.sub.3                                                                           N CH COCH.sub.3                         ##STR34##                                                                                         ##STR35##      OCH.sub.3                                                                           N CH COCH.sub.3                         ##STR36##                                                                                         ##STR37##      CH.sub.3                                                                            N CH CCH.sub.3                          ##STR38##                                                                                         ##STR39##      CH.sub.3                                                                            N CH C CH.sub.3                         ##STR40##                                                                                         ##STR41##      OCH.sub.3                                                                           N CH COCH.sub.3                         ##STR42##                                                                                         ##STR43##      OCH.sub.3                                                                           N CH COCH.sub.3                         ##STR44##                                                                                         ##STR45##      C.sub.2 H.sub.5                                                                     N CH COCH.sub.3                         ##STR46##                                                                                         ##STR47##      C.sub.2 H.sub.5                                                                     N CH COCH.sub.3                         ##STR48##                                                                                         ##STR49##      OCH.sub.3                                                                           N CH CCl                                ##STR50##                                                                                         ##STR51##      OCH.sub.3                                                                           N CH CCl                                ##STR52##                                                                                         ##STR53##      OCH.sub.3                                                                           N CH CCl                                ##STR54##                                                                                         ##STR55##      OCH.sub.3                                                                           N CH CCl                                ##STR56##                                                                                         ##STR57##      H    N CH CCH.sub.3                          ##STR58##                                                                                         ##STR59##      CH.sub.3                                                                            N CH COCH.sub.3                         ##STR60##                                                                                         ##STR61##      OCH.sub.3                                                                           N CH COCH.sub.3                         ##STR62##                                                                                         ##STR63##      CH.sub.3                                                                            N CH COCH.sub.3                         ##STR64##                                                                                         ##STR65##      OCH.sub.3                                                                           N CH COCH.sub.3                         ##STR66##                                                                                         ##STR67##      OCH.sub.3                                                                           N CH COCH.sub.3                         ##STR68##                                                                                         ##STR69##      CH.sub.3                                                                            N CH COC.sub.2 H.sub.5                  ##STR70##                                                                                         ##STR71##      OCHF.sub.2                                                                          N CH CCH.sub.3                          ##STR72##                                                                                         ##STR73##      CH.sub.3                                                                            N CH CSCH.sub.3                         ##STR74##                                                                                         ##STR75##      CH.sub.3                                                                            N CH CN(CH.sub.3).sub.2                 ##STR76##                                                                                         ##STR77##      OCHF.sub.2                                                                          N CH COCHF.sub.2                        ##STR78##                                                                                         ##STR79##      OCH.sub.3                                                                           N CH COCH.sub.3                         ##STR80##                                                                                         ##STR81##      OCH.sub.3                                                                           N N  COCH.sub.3                         ##STR82##                                                                                         ##STR83##      CH.sub.3                                                                            N N  COCH.sub.3                         ##STR84##                                                                                         ##STR85##      OCH.sub.3                                                                           N N  COCH.sub.3                         ##STR86##                                                                                         ##STR87##      OCH.sub.3                                                                           N N  COCH.sub.3                         ##STR88##                                                                                         ##STR89##      CH.sub.3                                                                            N N  COCH.sub.3                         ##STR90##                                                                                         ##STR91##      OCH.sub.3                                                                           N N  COCH.sub.3                         ##STR92##                                                                                         ##STR93##      CH.sub.3                                                                            N N  CCH.sub.3                          ##STR94##                                                                                         ##STR95##      CH.sub.3                                                                            N N  CCl                                ##STR96##                                                                                         ##STR97##      OCH.sub.3                                                                           N N  COCH.sub.3                         ##STR98##                                                                                         ##STR99##      OCH.sub.3                                                                           N N  COCH.sub.3                         ##STR100##                                                                                        ##STR101##     OCH.sub.3                                                                           N N  COCH.sub.3                         ##STR102##                                                                                        ##STR103##     OCH.sub.3                                                                           N CH COCH.sub.3                         ##STR104##                                                                                        ##STR105##     OCH.sub.3                                                                           N CH COCH.sub.3                        OC.sub.6 H.sub.5                                                                                   ##STR106##     CH.sub.3                                                                            N CH CCH.sub.3                         OCH.sub.3                                                                                          ##STR107##     CH.sub.3                                                                            N CH COCH.sub.3                        SCH.sub.3                                                                                          ##STR108##     OCH.sub. 3                                                                          N CH COCH.sub.3                        SC.sub.6 H.sub.5                                                                                   ##STR109##     OCH.sub.3                                                                           N CH COCH.sub.3                         ##STR110##                                                                                        ##STR111##     CH.sub.3                                                                            N N  COCH.sub.3                         ##STR112##                                                                                        ##STR113##     OCH.sub.3                                                                           N CH COCH.sub.3                         ##STR114##                                                                                        ##STR115##     OCH.sub.3                                                                           N CH COCH.sub.3                        __________________________________________________________________________

The starting materials of the formula (II) are known and/or can be prepared by processes which are known per se (compare EP-A 121,082, EP-A 172,957, EP-A 173,321, EP-A 173,956, EP-A 224,078, EP-A 5,986 and EP-A 24,215).

Formula (III) provides a general definition of the sulphonyl hydrazides to be used in addition as starting materials in the process according to the invention. In formula (III), R² preferably or particularly has those meanings which have already been given above as preferred or as particularly preferred for R² in the scope of the description of the compounds of the formula (I) according to the invention.

Examples of the compounds of the formula (III) which may be mentioned are: methane-, ethane-, propane- and butane-sulphonyl hydrazide, trifluoromethane-, perfluorobutane-, chloromethane-and 2-chloro-ethane-sulphonyl hydrazide, benzenesulphonyl hydrazide, 2-fluoro-, 4-fluoro-, 2-chloro-, 4-chloro-, 2-bromo-, 4-bromo-, 2-methyl-, 4-methyl-, 2-trifluoromethyl-, 3-chlorodifluoromethyl-, 2-methoxy-, 4-methoxy-, 2-ethoxy-, 4-ethoxy-, 2-difluoromethoxy-, 2-trifluoromethoxy-, 4-trifluoromethoxy-, 3-trifluoromethoxy-, 2-methoxycarbonyl-, 4-methoxycarbonyl-, 2-ethoxycarbonyl-, 4-ethoxycarbonyl-benzenesulphonyl hydrazide and dimethylsulphamoyl hydrazine.

The starting materials of the formula (III) are known and/or can be prepared by processes which are known per se (compare Org. Synth. 40 (1960), 93-95).

The process according to the invention for the preparation of the new sulphonylaminoguanidinoazines of the formula (I) is preferably carried out using diluents. Possible diluents here are preferably water and/or polar organic solvents, such as methanol, ethanol, isopropanol, butanol, isobutanol, sec-butanol, tert-butanol, glycol dimethyl ether, diglycol dimethyl ether, tetrahydrofuran, dioxane, methyl acetate, ethyl acetate, acetonitrile, propionitrile, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulphoxide and tetramethylenesulphone.

The reaction temperatures can be varied within a relatively wide range when carrying out the process according to the invention. In general, the reaction is carried out at temperatures between 0° C. and 150° C., preferably at temperatures between 10° C. and 100° C.

For carrying out the process according to the invention, between 1 and 5 mols, preferably about 1 and 3 mols, of sulphonyl hydrazide of the formula (III) are generally employed per mol of sulphonyl compound of the formula (II).

In general, the reaction components are combined at room temperature or with ice cooling and the reaction mixture is stirred until completion of the reaction, if necessary at elevated temperature. The products of the formula (I) are generally precipitated as crystals after cooling and can be isolated by filtering off with suction.

For conversion into salts, the compounds of the formula (I) in which M stands for hydrogen are stirred with suitable metal compounds, such as, for example, sodium hydroxide or potassium hydroxide, sodium methylate or potassium methylate, or sodium ethylate or potassium ethylate or with suitable amines, such as, for example, isopropylamine, in suitable diluents, such as, for example, water, methanol or ethanol. The salts can then be isolated - if appropriate after concentration, as crystalline products.

The active compounds according to the invention can be used as defoliants, desiccants, agents for destroying broad-leaved plants and, especially, as weed-killers. By weeds, in the broadest sense, there are to be understood all plants which grow in locations where they are undesired. Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used.

The active compounds according to the invention can be used, for example, in connection with the following plants:

Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver and Centaurea.

Dicotyledon cultures of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.

Monocotyledon weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus and Apera.

Monocotyledon cultures of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus and Allium.

However, the use of the active compounds according to the invention is in no way restricted to these genera, but also extends in the same manner to other plants.

The compounds are suitable, depending on the concentration, for the total combating of weeds, for example on industrial terrain and rail tracks, and on paths and squares with or without tree plantings. Equally, the compounds can be employed for combating weeds in perennial cultures, for example afforestations, decorative tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hopfields, and for the selective combating of weeds in annual cultures.

The new active compounds are suitable for selectively combating monocotyledon and dicotyledon weeds using the pre-emergence and the post-emergence methods, in particular in monocotyledon crops, particularly also paddy rice.

On application of the new active compounds, defoliant action and activity against rice diseases, such as Pyricularia oryzae, was also observed.

The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, pastes, soluble powders, granules, suspension-emulsion concentrates, natural and synthetic materials impregnated with active compound, and very fine capsules in polymeric substances.

These formulations are produced in known manner, for example by mixing the active compounds with extenders, that is liquid solvents and/or solid carriers, optionally with the use of surface-active agents, that is emulsifying agents and/or dispersing agents and/or foam-forming agents.

In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents. As liquid solvents, there are suitable in the main: aromatics, such as xylene, toluene or alkyl naphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide, as well as water.

As solid carriers there are suitable: for example ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly disperse silicic acid, alumina and silicates, as solid carriers for granules there are suitable: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; as emulsifying and/or foam-forming agents there are suitable: for example non-ionic and anionic emulsifiers, such as polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkylsulphates, arylsulphonates as well as albumin hydrolysation products; as dispersing agents there are suitable: for example lignin-sulphite waste liquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids, can be used in the formulations. Further additives can be mineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

The formulations in general contain between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90%.

The active compounds according to the invention, as such or in the form of their formulations, can also be used, for combating weeds, as mixtures with known herbicides, finished formulations or tank mixes being possible.

Possible components for the mixtures are known herbicides, such as, for example, 1-amino-6-ethylthio-3-(2,2-dimethylpropyl)-1,3,5-triazine-2,4(1H,3H)-dione or N-(2-benzothiazolyl)-N,N'-dimethylurea for combating weeds in cereals; 4-amino-3-methyl-6-phenyl-1,2,4-triazin-5(4H)-one for combating weeds in sugar beets, and 4-amino-6-(1,1-dimethylethyl)-3-methylthio-1,2,4-triazin-5(4H)-one for combating weeds in soy beans, and furthermore also 2,4-dichlorophenoxyacetic acid; 4-(2,4-dichlorophenoxy)-butyric acid; 2,4-dichlorophenoxypropionic acid; methyl 2-[[[[[(4,6-dimethoxypyrimidin-2-yl)-amino]-carbonyl]-amino]-sulphonyl]-methyl]-benzoate; 3-isopropyl-2,1,3-benzothiadiazin-4-one 2,2-dioxide; methyl 5-(2,4-dichlorophenoxy)-2-nitrobenzoate; 3,5-dibromo-4-hydroxy-benzonitrile; N-(butoxymethyl)-2-chloro-N-(2,6-diethylphenyl)-acetamide; 2-chloro-N-{[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-amino]-carbonyl}-benzenesulphonamide; N,N-dimethyl-N'-(3-chloro-4-methylphenyl)-urea; 2-[4-(2,4-dichlorophenoxy)-phenoxy]-propionic acid, its methyl or its ethyl ester; 3,6-dichloro-2-pyridinecarboxylic acid; 4-amino-6-t-butyl-3-ethylthio-1,2,4-triazin-5(4H)-one; 2-{4-[(6-chloro-2-benzoxazolyl)-oxy]-phenoxy}-propanoic acid, its methyl or its ethyl ester; trimethylsilylmethyl 2-[4-(3,5-dichloropyrid-2-yl-oxy)-phenoxy]-propionate; 2-(4,5-dihydro-4-methyl-4-isopropyl-5-oxo-1H-imidazol-2-yl)-pyridine-3-carboxylic acid; 3,5-diiodo-4-hydroxybenzonitrile; N,N-dimethyl-N'-(4-isopropylphenyl)-urea; (2-methyl-4-chlorophenoxy)-acetic acid; (4-chloro-2-methylphenoxy)-propionic acid; 2-{[[((4-methoxy-6-methyl-1,3,5-triazin-2-yl)-amino)-carbonyl]-amino]-sulphonyl}-benzoic acid or its methyl ester; S-ethyl N,N-hexamethylene-thiocarbamate; 4-(di-n-propylamino)-3,5-dinitrobenzenesulphonamide; N-(1-ethylpropyl)-3,4-dimethyl-2,6-dinitroaniline; α-chloro-2',6'-diethyl-N-(2-propoxyethyl)-acetanilide; 2-chloro-N-isopropylacetanilide; 4-ethylamino-2-t-butylamino-6-methylthio-s-triazine; methyl 3-[[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-amino]-carbonyl]-amino]-sulphonyl]-thiophene-2-carboxylate; N,N-diisopropyl-S-(2,3,3-trichloroallyl)-thiocarbamate and 3,5,6-trichloro-2-pyridyloxyacetic acid. Surprisingly, some mixtures also show a synergistic action.

Mixtures with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellents, plant nutrients and agents which improve soil structure, as also possible.

The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. They are used in the customary manner, for example by watering, spraying, atomizing or scattering.

The active compounds according to the invention can be applied either before or after emergence of the plants.

They can also be incorporated into the soil before sowing.

The amount of active compound used can vary within a relatively wide range. It depends essentially on the nature of the desired effect. In general, the amounts used are between 0.01 and 15 kg of active compound per hectare of soil surface, preferably between 0.05 and 10 kg per ha.

The preparation and use of the active compounds according to the invention can be seen from the following examples.

PREPARATION EXAMPLES Example 1 ##STR116##

A mixture of 6.5 g (0.01 mol) of N'-(4-methoxy-6-methyl-pyrimidin-2-yl)-N"-methoxy-N",N"'-bis-(2-bromophenylsulphonyl)-guanidine, 5.6 g (0.03 mol) of p-toluenesulphonyl hydrazide, 30 ml of ethanol and 10 ml of water is heated to boiling under reflux for 60 minutes and then stirred for 20 hours at 20° C. The precipitated crystalline product is isolated by filtering with suction.

3.1 g (51% of theory) of N'-(4-methoxy-6-methylpyrimidin-2-yl)-N"-(4-methyl-phenylsulphonylamino)-N"'-(2-bromo-phenylsulphonyl)-guanidine of melting point 156° C. are obtained.

The compounds of the formula (I) shown in Table 2 below can be prepared analogously to Example 1 and corresponding to the general description of the process according to the invention.

    TABLE 2       Examples of compounds of the formula (I)       ##STR117##       (I)       Example No. M R.sup.1 R.sup.2 R.sup.3 X Y Z Melting point (°C.)       2 H      ##STR118##       ##STR119##       CH.sub.3 N CH CCH.sub.3 153       3 H      ##STR120##       ##STR121##       OCH.sub.3 N CH COCH.sub.3 163       4 H      ##STR122##       ##STR123##       OCH.sub.3 N CH COCH.sub.3 110       5 H      ##STR124##       ##STR125##       OCH.sub.3 N CH COCH.sub.3 174       6 H      ##STR126##       ##STR127##       OCH.sub.3 N CH COCH.sub.3 177       7 H      ##STR128##       ##STR129##       OCH.sub.3 N CH COCH.sub.3 166       8 H      ##STR130##       ##STR131##       OCH.sub.3 N CH COCH.sub.3 102       9 H      ##STR132##       CH.sub.3 OCH.sub.3 N CH COCH.sub.3 174       10 H      ##STR133##       CH.sub.3 OCH.sub.3 N CH COCH.sub.3  87       11 H      ##STR134##       CH.sub.3 OCH.sub.3 N CH COCH.sub.3 184       12 H      ##STR135##       ##STR136##       OCH.sub.3 N CH COCH.sub.3 113       13 H      ##STR137##       C.sub.3 H.sub.7 OCH.sub.3 N CH COCH.sub.3 155       14 H      ##STR138##       ##STR139##       OCH.sub.3 N CH COCH.sub.3 147       15 H      ##STR140##       ##STR141##       OCH.sub.3 N CH COCH.sub.3 151       16 Na      ##STR142##       ##STR143##       OCH.sub.3 N CH COCH.sub.3       17 K      ##STR144##       ##STR145##       OCH.sub.3 N CH COCH.sub.3       18 H      ##STR146##       ##STR147##       OCH.sub.3 N CH COCH.sub.3       19 H      ##STR148##       ##STR149##       OCH.sub.3 N CH COCH.sub.3       20 H      ##STR150##       ##STR151##       OCH.sub.3 N CH COCH.sub.3       21 H      ##STR152##       ##STR153##       CH.sub.3 N CH COCH.sub.3 154       22 H      ##STR154##       ##STR155##       CH.sub.3 N CH COCH.sub.3 179  23 H.sub.3       NCH(CH.sub.3).sub.2      ##STR156##       ##STR157##       CH.sub.3 N CH COCH.sub.3  84       24 K      ##STR158##       ##STR159##       CH.sub.3 N CH COCH.sub.3 127       25 H      ##STR160##       ##STR161##       CH.sub.3 N CH COC.sub.2 H.sub.5 155       26 H      ##STR162##       CH.sub.3 CH.sub.3 N CH COCH.sub.3 178       27 H      ##STR163##       ##STR164##       CH.sub.3 N CH COCH.sub.3 182       28 H      ##STR165##       ##STR166##       CH.sub.3 N CH COC.sub.2 H.sub.5       29 H      ##STR167##       ##STR168##       C.sub.2 H.sub.5 N CH COCH.sub.3 173       30 H      ##STR169##       ##STR170##       CH.sub.3 N CH COCH.sub.3       31 H      ##STR171##       ##STR172##       CH.sub.3 N CH COCH.sub.3       32 H      ##STR173##       CH.sub.3 CH.sub.3 N CH COCH.sub.3       33 H      ##STR174##       CH.sub.3 CH.sub.3 N CH COCH.sub.3       34 H      ##STR175##       ##STR176##       CH.sub.3 N CH COCH.sub.3       35 H      ##STR177##       ##STR178##       CH.sub.3 N N COCH.sub.3 183       36 H      ##STR179##       CH.sub.3 CH.sub.3 N N COCH.sub.3       37 H      ##STR180##       ##STR181##       OCH.sub.3 N N COCH.sub.3       38 H      ##STR182##       CH.sub.3 OCH.sub.3 N N COCH.sub.3       39 H      ##STR183##       CH.sub.3 OCH.sub.3 N N COCH.sub.3       40 H      ##STR184##       ##STR185##       OCH.sub.3 N N COCH.sub.3       41 H      ##STR186##       CH.sub.3 OCH.sub.3 N N COCH.sub.3       42 H      ##STR187##       ##STR188##       CH.sub.3 N N CCH.sub.3       43 H      ##STR189##       CH.sub.3 OCH.sub.3 N N COCH.sub.3       44 H      ##STR190##       ##STR191##       OCH.sub.3 N N COCH.sub.3       45 H      ##STR192##       CH.sub.3 OCH.sub.3 N N COCH.sub.3       46 H      ##STR193##       ##STR194##       CH.sub.3 N N COCH.sub.3       47 H      ##STR195##       ##STR196##       CH.sub.3 N N COCH.sub.3       48 H      ##STR197##       ##STR198##       OCH.sub.3 N N COCH.sub.3       49 H      ##STR199##       ##STR200##       C.sub.2 H.sub.5 N N COCH.sub.3       50 H      ##STR201##       ##STR202##       CH.sub.3 N N COC.sub.2 H.sub.5       51 H      ##STR203##       ##STR204##       OCH.sub.3 N CH COCH.sub.3 223       52 H      ##STR205##       ##STR206##       OCH.sub.3 N CH COCH.sub.3 100       53 H      ##STR207##       ##STR208##       OCH.sub.3 N CH COCH.sub.3 218       54 H      ##STR209##       ##STR210##       OCH.sub.3 N CH COCH.sub.3 112       55 H      ##STR211##       ##STR212##       CH.sub.3 N N COCH.sub.3       56 H      ##STR213##       ##STR214##       OCH.sub.3 N N COCH.sub.3       57 H      ##STR215##       ##STR216##       OCH.sub.3 N N COCH.sub.3       58 H      ##STR217##       ##STR218##       CH.sub.3 N CH CCH.sub.3       59 H      ##STR219##       ##STR220##       CH.sub.3 N CH CCH.sub.3       60 H      ##STR221##       ##STR222##       OCH.sub.3 N CH COCH.sub.3       61 H      ##STR223##       ##STR224##       CH.sub.3 N CH CCH.sub.3       62 H      ##STR225##       ##STR226##       OCH.sub.3 N CH COCH.sub.3       63 H      ##STR227##       ##STR228##       OCH.sub.3 N N COCH.sub.3        64 H      ##STR229##       ##STR230##       OCH.sub.3 N N COCH.sub.3       65 H      ##STR231##       ##STR232##       CH.sub.3 N CH CCH.sub.3       66 H      ##STR233##       ##STR234##       CH.sub.3 N CH CCH.sub.3       67 H      ##STR235##       ##STR236##       CH.sub.3 N CH CCH.sub.3       68 H      ##STR237##       ##STR238##       OCH.sub.3 N CH COCH.sub.3       69 H      ##STR239##       ##STR240##       OCH.sub.3 N CH COCH.sub.3       70 H      ##STR241##       ##STR242##       OCH.sub.3 N CH CCl       71 H      ##STR243##       C.sub.3 H.sub.7 -n OCH.sub.3 N CH CCl       72 H      ##STR244##       N(CH.sub.3).sub.2 OCH.sub.3 N CH COCH.sub.3 158       73 H      ##STR245##       ##STR246##       OCH.sub.3 N CH COCH.sub.3       74 H      ##STR247##       CH.sub.3 OCH.sub.3 N CH COCH.sub.3       75 H      ##STR248##       C.sub.3 H.sub.7 -n OCH.sub.3 N CH COCH.sub.3       76 H      ##STR249##       ##STR250##       OCH.sub.3 N CH COCH.sub.3       77 H      ##STR251##       N(CH.sub.3).sub.2 OCH.sub.3 N CH COCH.sub.3       78 H      ##STR252##       ##STR253##       OCH.sub.3 N CH CCl       79 H      ##STR254##       ##STR255##       CH.sub.3 N N COCH.sub.3       80 H      ##STR256##       ##STR257##       OCH.sub.3 N CH COCH.sub.3       81 H      ##STR258##       ##STR259##       OCHF.sub.2 N CH COCHF.sub.2       82 H      ##STR260##       ##STR261##       OCH.sub.3 N CH CH(OCH.sub.3).sub.2       83 H      ##STR262##       ##STR263##       OCH.sub.3 N CH COCH.sub.3       84 H      ##STR264##       ##STR265##       OCH.sub.3 N CH COCH.sub.3       85 H      ##STR266##       ##STR267##       OCH.sub.3 N N COCH.sub.3       86 H      ##STR268##       ##STR269##       OCH.sub.3 N CH COCH.sub.3       87 H      ##STR270##       C.sub.3 H.sub.7 -n OCH.sub.3 N CH COCH.sub.3       88 H      ##STR271##       ##STR272##       OCH.sub.3 N CH COCH.sub.3       89 H      ##STR273##       ##STR274##       OCH.sub.3 N N COCH.sub.3       90 H      ##STR275##       ##STR276##       OCH.sub.3 N N COCH.sub.3       91 H      ##STR277##       ##STR278##       NHCH.sub.3 N N COC.sub.2 H.sub.5       92 H      ##STR279##       CH.sub.3 NHCH.sub.3 N N COC.sub.2 H.sub.5       93 H      ##STR280##       ##STR281##       NHCH.sub.3 N N CC.sub.2 H.sub.5       94 H      ##STR282##       ##STR283##       NHCH.sub.3 N N COC.sub.2 H.sub.5       95 H      ##STR284##       ##STR285##       OCH.sub.3 N CH COCH.sub.3 164       96 H      ##STR286##       ##STR287##       CH.sub.3 N CH COCH.sub.3 202       97 H      ##STR288##       ##STR289##       CH.sub.3 N CH COCH.sub.3 181       98 H      ##STR290##       ##STR291##       CH.sub.3 N CH COCH.sub.3 148       99 H      ##STR292##       ##STR293##       CH.sub.3 N CH COC.sub.2 H.sub.5 106  100        H      ##STR294##       CH.sub.3 OCH.sub.3 N CH COCH.sub.3  101        H      ##STR295##       ##STR296##       OCH.sub.3 N CH COCH.sub.3  102        H      ##STR297##       ##STR298##       OCH.sub.3 N CH CCl  103        H      ##STR299##       ##STR300##       CF.sub.3 N CH COCH.sub.3  63  104        H      ##STR301##       ##STR302##       CH.sub.3 N CH CCH.sub.3 157  105        H      ##STR303##       ##STR304##       OCH.sub.3 N CH COCH.sub.3 211  106        H      ##STR305##       ##STR306##       OCH.sub.3 N CH COCH.sub.3 147  107        H      ##STR307##       ##STR308##       OCH.sub.3 N CH COCH.sub.3  108        H      ##STR309##       ##STR310##       OCH.sub.3 N CH COCH.sub.3 160  109        H      ##STR311##       ##STR312##       CH.sub.3 N CH COCH.sub.3 168  110        H      ##STR313##       ##STR314##       CH.sub.3 N CH CCH.sub.3 159  111        H      ##STR315##       ##STR316##       OCH.sub.3 N N COCH.sub.3 188  112        H      ##STR317##       ##STR318##       OCH.sub.3 N N COCH.sub.3 176  113        H      ##STR319##       ##STR320##       OCH.sub.3 N N COCH.sub.3 198  114        H      ##STR321##       ##STR322##       OCH.sub.3 N N COCH.sub.3 172  115        H      ##STR323##       ##STR324##       CH.sub.3 N N COCH.sub.3 139  116        H      ##STR325##       ##STR326##       OCH.sub.3 N N COCH.sub.3 173  117        H      ##STR327##       ##STR328##       OCH.sub.3 N N COCH.sub.3 115

The compounds of the formula (Ia) shown in Table 3 below can also be prepared analogously to Example 1 and corresponding to the general description of the process according to the invention.

The compounds of the formula (Ia) are a subgroup of the compounds of the formula (I). ##STR329##

                                      TABLE 3                                      __________________________________________________________________________     Examples of compounds of the formula (Ia)                                      Example             Position             Melting                               No.  R.sup.1        COR.sup.2   R.sup.3                                                                            R.sup.5                                                                             point (°C.)                    __________________________________________________________________________     118                                                                                                (2-)COOCH.sub.3                                                                            OCH.sub.3                                                                          OCH.sub.3                                                                           162                                   119                                                                                  ##STR330##    (2-)COOCH(CH.sub.3).sub.2                                                                  OCH.sub.3                                                                          OCH.sub.3                                                                           134                                   120                                                                                  ##STR331##    (2-)COOCH.sub.3                                                                            CH.sub.3                                                                           OCH.sub.3                                                                           149                                   121                                                                                  ##STR332##    (2-)COOCH.sub.3                                                                            OCH.sub.3                                                                          OCH.sub.3                                                                            97                                   122                                                                                  ##STR333##    (2-)COOCH.sub.3                                                                            OCH.sub.3                                                                          OCH.sub.3                                                                           145                                   123                                                                                  ##STR334##    (2-)COOCH.sub.3                                                                            CH.sub.3                                                                           OCH.sub.3                                                                           132                                   124                                                                                  ##STR335##    (2-)COOCH.sub.3                                                                            OCH.sub.3                                                                          OCH.sub.3                                                                           163                                   125                                                                                  ##STR336##    (2-)COOC.sub.2 H.sub.5                                                                     OCH.sub.3                                                                          OCH.sub.3                                                                           162                                   126                                                                                  ##STR337##    (2-)COOCH.sub.3                                                                            CH.sub.3                                                                           OCH.sub.3                                                                           189                                   127                                                                                  ##STR338##    (2-)COOC.sub.2 H.sub.5                                                                     CH.sub.3                                                                           OCH.sub.3                                                                           176                                   128                                                                                  ##STR339##    (2-)COOCH.sub.3                                                                            CH.sub.3                                                                           OCH.sub.3                                                                           184                                   129                                                                                  ##STR340##    (2-)COOC.sub.2 H.sub.5                                                                     CH.sub.3                                                                           OCH.sub.3                                                                           126                                   130                                                                                  ##STR341##    (2-)COOC.sub.2 H.sub.5                                                                     OCH.sub.3                                                                          OCH.sub.3                                                                            84                                   131                                                                                  ##STR342##    (2-)COOCH.sub.3                                                                            CH.sub.3                                                                           OCH.sub.3                                                                           192                                   132                                                                                  ##STR343##    (2-)COOC.sub.2 H.sub.5                                                                     CH.sub.3                                                                           OCH.sub.3                                                                           167                                   133                                                                                  ##STR344##    (2-)COOC.sub.2 H.sub.5                                                                     OCH.sub.3                                                                          OCH.sub.3                                                                           125                                   134                                                                                  ##STR345##    (2-)COOCH.sub.3                                                                            OCH.sub.3                                                                          OCH.sub.3                                                                           140                                   135                                                                                  ##STR346##    (2-)COOC.sub.2 H.sub.5                                                                     OCH.sub.3                                                                          OCH.sub.3                                                                           150                                   136                                                                                  ##STR347##    (2-)COOCH.sub.3                                                                            OCH.sub.3                                                                          OCH.sub.3                                                                           197                                   137                                                                                  ##STR348##    (2-)COOC.sub.2 H.sub.5                                                                     OCH.sub.3                                                                          OCH.sub.3                                                                           190                                   138                                                                                  ##STR349##    (2-)COOCH.sub.3                                                                            OCH.sub.3                                                                          OCH.sub.3                                                                           177                                   139                                                                                  ##STR350##    (2-)COOC.sub.2 H.sub.5                                                                     OCH.sub.3                                                                          OCH.sub.3                                                                           137                                   140                                                                                  ##STR351##    (2-)COOCH.sub.3                                                                            CH.sub.3                                                                           OCH.sub.3                                                                           167                                   141                                                                                  ##STR352##    (2-)COOC.sub.2 H.sub.5                                                                     CH.sub.3                                                                           OCH.sub.3                                                                           160                                   142                                                                                  ##STR353##    (2-)COOCH.sub.3                                                                            CH.sub.3                                                                           OCH.sub.3                                                                           149                                   143                                                                                  ##STR354##    (2-)COOCH.sub.3                                                                            OCH.sub.3                                                                          OCH.sub.3                                                                           173                                   144                                                                                  ##STR355##    (2-)COOC.sub.2 H.sub.5                                                                     OCH.sub.3                                                                          OCH.sub.3                                                                           182                                   145                                                                                  ##STR356##    (2-)COOCH.sub.3                                                                            CH.sub.3                                                                           OCH.sub.3                                                                           149                                   146                                                                                  ##STR357##    (2-)COOC.sub.2 H.sub.5                                                                     CH.sub.3                                                                           OCH.sub.3                                                                           142                                   147                                                                                  ##STR358##    (2-)COOCH.sub.3                                                                            CH.sub.3                                                                           OCH.sub.3                                                                           131                                   148                                                                                  ##STR359##    (2-)COOC.sub.2 H.sub.5                                                                     CH.sub.3                                                                           OCH.sub.3                                                                           119                                   149                                                                                  ##STR360##    (2-)COOCH.sub.3                                                                            CH.sub.3                                                                           OCH.sub.3                                                                           159                                   150                                                                                  ##STR361##    (2-)COOC.sub.2 H.sub.5                                                                     CH.sub.3                                                                           OCH.sub.3                                                                           172                                   151                                                                                  ##STR362##    (2-)COOCH.sub.3                                                                            OCH.sub.3                                                                          OCH.sub.3                                                                           186                                   152                                                                                  ##STR363##    (2-)COOC.sub.2 H.sub.5                                                                     OCH.sub.3                                                                          OCH.sub.3                                                                           176                                   153                                                                                  ##STR364##    (2-)COOCH.sub.3                                                                            OCH.sub.3                                                                          OCH.sub.3                                                                           116                                   154                                                                                  ##STR365##    (2-)COOC.sub.2 H.sub.5                                                                     OCH.sub.3                                                                          OCH.sub.3                                                                            88                                   155                                                                                  ##STR366##    (2-)COOC.sub.2 H.sub.5                                                                     CH.sub.3                                                                           OCH.sub.3                                                                            91                                   156                                                                                  ##STR367##    (2-)COOCH.sub.3                                                                            CH.sub.3                                                                           OCH.sub.3                                                                           119                                   157                                                                                  ##STR368##    (2-)COOC.sub.2 H.sub.5                                                                     CH.sub.3                                                                           OCH.sub.3                                                                            87                                   158                                                                                  ##STR369##    (2-)COOCH.sub.3                                                                            CH.sub.3                                                                           OCH.sub.3                                                                            82                                   159                                                                                  ##STR370##    (2-)COOCH.sub.3                                                                            OCH.sub.3                                                                          OCH.sub.3                                                                            93                                   160                                                                                  ##STR371##    (2-)COOC.sub.2 H.sub.5                                                                     OCH.sub.3                                                                          OCH.sub.3                                                                           158                                   161                                                                                  ##STR372##    (2-)COOC.sub.3 H.sub.7 n                                                                   CH.sub.3                                                                           OCH.sub.3                                                                            95                                   162                                                                                  ##STR373##    (2-)COOCH(CH.sub.3).sub.2                                                                  CH.sub.3                                                                           OCH.sub.3                                                                           104                                   163                                                                                  ##STR374##    (2-)COOCH.sub.2 CH.sub.2 OCH.sub.3                                                         CH.sub.3                                                                           OCH.sub.3                                                                           105                                   164                                                                                  ##STR375##    (2-)-COOCH.sub.2 CH.sub.2 Cl                                                               CH.sub.3                                                                           OCH.sub.3                                                                           104                                   165                                                                                  ##STR376##    (2-)COOC.sub.3 H.sub. 7 n                                                                  OCH.sub.3                                                                          OCH.sub.3                                                                            80                                   166                                                                                  ##STR377##    (2-)COOCH(CH.sub.3).sub.2                                                                  OCH.sub.3                                                                          OCH.sub.3                                                                            80                                   167                                                                                  ##STR378##    (2-)COOCH.sub.2 CH.sub.2 OCH.sub.3                                                         OCH.sub.3                                                                          OCH.sub.3                                                                            84                                   168                                                                                  ##STR379##    (2-)COOCH.sub.2 CH.sub.2 Cl                                                                OCH.sub.3                                                                          OCH.sub.3                                                                            84                                   169                                                                                  ##STR380##    (2-)COOCH.sub.2 CH.sub.2 OCH.sub.3                                                         OCH.sub.3                                                                          OCH.sub.3                                                                           160                                   170                                                                                  ##STR381##    (2-)COOCH(CH.sub.3).sub.2                                                                  OCH.sub.3                                                                          OCH.sub.3                                                                            87                                   171                                                                                  ##STR382##    (2-)COOC.sub.3 H.sub.7 n                                                                   OCH.sub.3                                                                          OCH.sub.3                                                                           134                                   172                                                                                  ##STR383##    (2-)COOCH.sub.2 CH.sub.2 Cl                                                                OCH.sub.3                                                                          OCH.sub.3                                                                            93                                   173                                                                                  ##STR384##    (2-)COOC.sub.3 H.sub.7 n                                                                   CH.sub.3                                                                           OCH.sub.3                                                                            87                                   174                                                                                  ##STR385##    (2-)COOCH(CH.sub.3).sub.2                                                                  CH.sub.3                                                                           OCH.sub.3                                                                            95                                   175                                                                                  ##STR386##    (2-)COOC.sub.3 H.sub.7 n                                                                   CH.sub.3                                                                           OCH.sub.3                                                                           120                                   176                                                                                  ##STR387##    (2-)COOCH(CH.sub.3).sub.2                                                                  CH.sub.3                                                                           OCH.sub.3                                                                            81                                   177                                                                                  ##STR388##    (2-)COOCH.sub.2 CH.sub.2 OCH.sub.3                                                         CH.sub.3                                                                           OCH.sub.3                                                                            82                                   178                                                                                  ##STR389##    (2-)COOCH.sub.2 CH.sub.2 Cl                                                                CH.sub.3                                                                           OCH.sub.3                                                                            89                                   179                                                                                  ##STR390##    (2-)COOCH.sub.2 CH.sub.2 OCH.sub.3                                                         CH.sub.3                                                                           OCH.sub.3                                                                            84                                   180                                                                                  ##STR391##    (2-)COOCH.sub.2 CH.sub.2 Cl                                                                CH.sub.3                                                                           OCH.sub.3                                                                           116                                   181                                                                                  ##STR392##    (2-)COOCH.sub.3                                                                            OCH.sub.3                                                                          OCH.sub. 3                                                                           95                                   182                                                                                  ##STR393##    (2-)COOC.sub.2 H.sub.5                                                                     OCH.sub.3                                                                          OCH.sub.3                                                                            86                                   183                                                                                  ##STR394##    (2-)COOC.sub.2 H.sub.5                                                                     CH.sub.3                                                                           OCH.sub.3                                                                            98                                   184                                                                                  ##STR395##    (2-)COOCH.sub.3                                                                            OCH.sub.3                                                                          OCH.sub.3                                                                           109                                   185                                                                                  ##STR396##    (2-)COOC.sub.2 H.sub.5                                                                     OCH.sub.3                                                                          OCH.sub.3                                                                           105                                   186                                                                                  ##STR397##    (2-)COOCH.sub.3                                                                            OCH.sub.3                                                                          OCH.sub.3                                                                            83                                   187                                                                                  ##STR398##    (2-)COOCH.sub.3                                                                            OCH.sub.3                                                                          OCH.sub.3                                                                            93                                   188                                                                                  ##STR399##    (2-)COOCH.sub.3                                                                            OCH.sub.3                                                                          OCH.sub.3                                                                            95                                   189                                                                                  ##STR400##    (2-)COOCH.sub.3                                                                            OCH.sub.3                                                                          OCH.sub.3                                                                            80                                   190                                                                                  ##STR401##    (2-)COOC.sub.2 H.sub.5                                                                     OCH.sub.3                                                                          OCH.sub.3                                                                           123                                   191                                                                                  ##STR402##    (2-)COOC.sub.2 H.sub.5                                                                     OCH.sub.3                                                                          OCH.sub.3                                                                            87                                   192                                                                                  ##STR403##    (2-)COOCH.sub.3                                                                            OCH.sub.3                                                                          OCH.sub.3                                                                            93                                   193                                                                                  ##STR404##    (2-)COOCH.sub.2 CH.sub.2 Cl                                                                OCH.sub.3                                                                          OCH.sub.3                                                                            95                                   194                                                                                  ##STR405##    (2-)COOCH.sub.3                                                                            CH.sub.3                                                                           OCH.sub.3                                                                            91                                   195                                                                                  ##STR406##    (2-)COOC.sub.2 H.sub.5                                                                     CH.sub.3                                                                           OCH.sub.3                                                                            86                                   196                                                                                  ##STR407##    (2-)COOC.sub.3 H.sub.7 n                                                                   CH.sub.3                                                                           OCH.sub.3                                                                           160                                   197                                                                                  ##STR408##    (2-)COOCH.sub.2 CH.sub.2 Cl                                                                CH.sub.3                                                                           OCH.sub.3                                                                            86                                   198                                                                                  ##STR409##    (2-)COOCH.sub. 3                                                                           CH.sub.3                                                                           OCH.sub.3                                                                            86                                   199                                                                                  ##STR410##    (2-)COOC.sub.2 H.sub.5                                                                     CH.sub.3                                                                           OCH.sub.3                                                                            86                                   200                                                                                  ##STR411##    (2-)COOC.sub.3 H.sub.7 n                                                                   CH.sub.3                                                                           OCH.sub.3                                                                            90                                   201                                                                                  ##STR412##    (2-)COOCH.sub.2 CH.sub.2 Cl                                                                CH.sub.3                                                                           OCH.sub.3                                                                            94                                   202                                                                                  ##STR413##    (2-)COOC.sub.3 H.sub.7 n                                                                   OCH.sub.3                                                                          OCH.sub.3                                                                           169                                   203                                                                                  ##STR414##    (2-)COOCH(CH.sub.3).sub.2                                                                  OCH.sub.3                                                                          OCH.sub.3                                                                            89                                   204                                                                                  ##STR415##    (2-)COOCH.sub.2 CH.sub.2 Cl                                                                OCH.sub.3                                                                          OCH.sub.3                                                                           153                                   205                                                                                  ##STR416##    (2-)COOCH.sub.3                                                                            CH.sub.3                                                                           SCH.sub.3                                                                            94                                   206                                                                                  ##STR417##    (2-)COOC.sub.2 H.sub.5                                                                     CH.sub.3                                                                           SCH.sub.3                                                                            94                                   207                                                                                  ##STR418##    (2-)COOCH.sub.3                                                                            OCH.sub.3                                                                           ##STR419##                                                                         135                                   208                                                                                  ##STR420##    (2-)COOCH.sub.3                                                                            OCH.sub.3                                                                           ##STR421##                                                                          98                                   209                                                                                  ##STR422##    (2-)COOC.sub.3 H.sub.7 n                                                                   CH.sub.3                                                                           OCH.sub.3                                                                            92                                   210                                                                                  ##STR423##    (2-)COOCH.sub.3                                                                            CH.sub.3                                                                           OCH.sub.3                                                                           108                                   211                                                                                  ##STR424##    (2-)COOCH.sub.3                                                                            CH.sub.3                                                                           OCH.sub.3                                                                           100                                   212                                                                                  ##STR425##    (2-)COOC.sub.2 H.sub.5                                                                     CH.sub.3                                                                           OCH.sub.3                                                                            86                                   213                                                                                  ##STR426##    (2-)COOC.sub.3 H.sub.7 n                                                                   CH.sub.3                                                                           OCH.sub.3                                                                            80                                   214                                                                                  ##STR427##    (2-)COOCH.sub.3                                                                            CH.sub.3                                                                           OCH.sub.3                                                                            87                                   215                                                                                  ##STR428##    (2-)COOC.sub.2 H.sub.5                                                                     CH.sub.3                                                                           OCH.sub.3                                                                            75                                   216                                                                                  ##STR429##    (2-)COOC.sub.3 H.sub.7 n                                                                   CH.sub.3                                                                           OCH.sub.3                                                                            78                                   217                                                                                  ##STR430##    (2-)COOCH(CH.sub.3).sub.2                                                                  CH.sub.3                                                                           OCH.sub.3                                                                            78                                   218                                                                                  ##STR431##    (2-)COOCH.sub.2 CH.sub.2 OCH.sub.3                                                         CH.sub.3                                                                           OCH.sub.3                                                                            79                                   219                                                                                  ##STR432##    (2-)COOCH.sub.3                                                                            OCH.sub.3                                                                          OCH.sub.3                                                                            83                                   220                                                                                  ##STR433##    (2-)COOC.sub.2 H.sub.5                                                                     OCH.sub.3                                                                          OCH.sub.3                                                                            82                                   221                                                                                  ##STR434##    (2-)COOC.sub.3 H.sub.7 n                                                                   OCH.sub.3                                                                          OCH.sub.3                                                                           136                                   222                                                                                  ##STR435##    (2-)COOCH(CH.sub.3).sub.2                                                                  OCH.sub.3                                                                          OCH.sub.3                                                                            76                                   223                                                                                  ##STR436##    (2-)COOCH(CH.sub.3).sub.2                                                                  CH.sub.3                                                                           OCH.sub.3                                                                            80                                   224                                                                                  ##STR437##    (2-)COOCH.sub.2 CH.sub.2 Cl                                                                OCH.sub.3                                                                          OCH.sub.3                                                                            79                                   225                                                                                  ##STR438##    (2-)COOCH.sub.2 CH.sub.2 OCH.sub.3                                                         OCH.sub.3                                                                          OCH.sub.3                                                                            75                                   226                                                                                  ##STR439##    (2-)COOCH.sub.3                                                                            CH.sub.3                                                                           OCH.sub.3                                                                            79                                   227                                                                                  ##STR440##    (2-)COOC.sub.2 H.sub.5                                                                     CH.sub.3                                                                           OCH.sub.3                                                                           115                                   228                                                                                  ##STR441##    (2-)COOC.sub.3 H.sub.7 n                                                                   CH.sub.3                                                                           OCH.sub.3                                                                           106                                   229                                                                                  ##STR442##    (2-)COOCH(CH.sub.3).sub.2                                                                  CH.sub.3                                                                           OCH.sub.3                                                                            71                                   230                                                                                  ##STR443##    (2-)COOCH.sub.2 CH.sub.2 Cl                                                                CH.sub.3                                                                           OCH.sub.3                                                                            75                                   231                                                                                  ##STR444##    (2-)COOCH.sub.2 CH.sub.2 OCH.sub.3                                                         CH.sub.3                                                                           OCH.sub.3                                                                            68                                   232                                                                                  ##STR445##    (2-)COOCH(CH.sub.3).sub.2                                                                  CH.sub.3                                                                           OCH.sub.3                                                                            72                                   233                                                                                  ##STR446##    (2-)COOCH.sub.2 CH.sub.2 OCH.sub.3                                                         CH.sub.3                                                                           OCH.sub.3                                                                            80                                   234                                                                                  ##STR447##    (2-)COOCH.sub.3                                                                            C.sub.2 H.sub.5                                                                    OCH.sub.3                                                                            78                                   235                                                                                  ##STR448##    (2-)COOC.sub.2 H.sub.5                                                                     C.sub.2 H.sub.5                                                                    OCH.sub.3                                                                            75                                   236                                                                                  ##STR449##    (2-)COOCH.sub.3                                                                            CH.sub.3                                                                           OC.sub.2 H.sub.5                                                                     98                                   237                                                                                  ##STR450##    (2-)COOC.sub. 2 H.sub.5                                                                    CH.sub.3                                                                           OC.sub.2 H.sub.5                                                                     94                                   238                                                                                  ##STR451##    (2-)COOCH.sub.3                                                                            C.sub.2 H.sub.5                                                                    OCH.sub.3                                                                            93                                   239                                                                                  ##STR452##    (2-)COOC.sub.2 H.sub.5                                                                     C.sub.2 H.sub.5                                                                    OCH.sub.3                                                                            78                                   240                                                                                  ##STR453##    (2-)COOCH.sub.3                                                                            CH.sub.3                                                                           OC.sub.2 H.sub.5                                                                     92                                   241                                                                                  ##STR454##    (2-)COOC.sub.2 H.sub.5                                                                     CH.sub.3                                                                           OC.sub.2 H.sub.5                                                                     81                                   242                                                                                  ##STR455##    (2-)COOCH.sub.3                                                                            CH.sub.3                                                                           SCH.sub.3                                                                           174                                   243                                                                                  ##STR456##    (2-)COOC.sub.2 H.sub.5                                                                     CH.sub.3                                                                           SCH.sub.3                                                                            82                                   244                                                                                  ##STR457##    (2-)COOCH.sub.3                                                                            CH.sub.3                                                                           SCH.sub.3                                                                            85                                   245                                                                                  ##STR458##    (2-)COOC.sub.2 H.sub.5                                                                     CH.sub.3                                                                           SCH.sub.3                                                                            80                                   246                                                                                  ##STR459##    (2-)COOCH.sub.3                                                                            CH.sub.3                                                                           SCH.sub.3                                                                            95                                   247                                                                                  ##STR460##    (2-)COOC.sub.2 H.sub.5                                                                     CH.sub.3                                                                           SCH.sub.3                                                                           120                                   248                                                                                  ##STR461##    (2-)COOCH.sub.3                                                                            CH.sub.3                                                                           OC.sub.2 H.sub.5                                                                     98                                   249                                                                                  ##STR462##    (2-)COOC.sub.2 H.sub.5                                                                     CH.sub.3                                                                           OC.sub.2 H.sub.5                                                                     93                                   250                                                                                  ##STR463##    (2-)COOCH.sub.3                                                                            C.sub.2 H.sub.5                                                                    OCH.sub.3                                                                            84                                   251                                                                                  ##STR464##    (2-)COOC.sub.2 H.sub.5                                                                     C.sub.2 H.sub.5                                                                    OCH.sub.3                                                                            83                                   252                                                                                  ##STR465##    (2-)COOCH.sub.3                                                                            CH.sub.3                                                                           OC.sub.2 H.sub.5                                                                    157                                   253                                                                                  ##STR466##    (2-)COOC.sub.3 H.sub.7 n                                                                   OCH.sub.3                                                                          OCH.sub.3                                                                           158                                   254                                                                                  ##STR467##    (2-)COOCH(CH.sub.3).sub.2                                                                  OCH.sub.3                                                                          OCH.sub.3                                                                           172                                   255                                                                                  ##STR468##    (2-)COOCH.sub.2 CH.sub.2 Cl                                                                OCH.sub.3                                                                          OCH.sub.3                                                                           156                                   256                                                                                  ##STR469##    (2-)COOCH.sub.2 CH.sub.2 OCH.sub.3                                                         OCH.sub.3                                                                          OCH.sub.3                                                                           119                                   257                                                                                  ##STR470##    (2-)COOCH.sub.3                                                                            CH.sub.3                                                                           OCH.sub.3                                                                           159                                   258                                                                                  ##STR471##    (2-)COOC.sub.2 H.sub.5                                                                     CH.sub.3                                                                           OCH.sub.3                                                                           141                                   259                                                                                  ##STR472##    (2-)COOC.sub.2 H.sub.5                                                                     CH.sub.3                                                                           OCH.sub.3                                                                           158                                   260                                                                                  ##STR473##    (2-)COOC.sub.3 H.sub.7 n                                                                   CH.sub.3                                                                           OCH.sub.3                                                                           159                                   261                                                                                  ##STR474##    (2-)COOCH(CH.sub.3).sub.2                                                                  CH.sub.3                                                                           OCH.sub.3                                                                           131                                   262                                                                                  ##STR475##    (2-)COOCH.sub.2 CH.sub.2 OCH.sub.3                                                         CH.sub.3                                                                           OCH.sub.3                                                                            91                                   263                                                                                  ##STR476##    (2-)COOC.sub.2 H.sub.5                                                                     OCH.sub.3                                                                          OCH.sub.3                                                                           164                                   264                                                                                  ##STR477##    (2-)COOC.sub.3 H.sub.7 n                                                                   OCH.sub.3                                                                          OCH.sub.3                                                                           148                                   265                                                                                  ##STR478##    (2-)COOCH(CH.sub.3).sub.2                                                                  OCH.sub.3                                                                          OCH.sub.3                                                                           183                                   266                                                                                  ##STR479##    (2-)COOCH.sub.2 CH.sub.2 Cl                                                                OCH.sub.3                                                                          OCH.sub.3                                                                           156                                   267                                                                                  ##STR480##    (2-)COOCH.sub.3                                                                            OCH.sub.3                                                                          OCH.sub.3                                                                           143                                   268                                                                                  ##STR481##    (2-)COOC.sub.2 H.sub.5                                                                     OCH.sub.3                                                                          OCH.sub.3                                                                           152                                   269                                                                                  ##STR482##    (2-)COOCH(CH.sub.3).sub.2                                                                  OCH.sub.3                                                                          OCH.sub.3                                                                           163                                   270                                                                                  ##STR483##    (2-)COOCH.sub.2 CH.sub.2 Cl                                                                OCH.sub.3                                                                          OCH.sub.3                                                                           168                                   271                                                                                  ##STR484##    (2-)COOCH.sub.2 CH.sub.2 OCH.sub.3                                                         OCH.sub.3                                                                          OCH.sub.3                                                                           152                                   272                                                                                  ##STR485##    (2-)COOCH.sub.3                                                                            OCH.sub.3                                                                          OCH.sub.3                                                                            88                                   273                                                                                  ##STR486##    (2-)COOC.sub.2 H.sub.5                                                                     OCH.sub.3                                                                          OCH.sub.3                                                                           123                                   274                                                                                  ##STR487##    (2-)COOC.sub.3 H.sub.7 n                                                                   OCH.sub.3                                                                          OCH.sub.3                                                                           117                                   275                                                                                  ##STR488##    (2-)COOCH(CH.sub.3).sub.2                                                                  OCH.sub.3                                                                          OCH.sub.3                                                                           138                                   276                                                                                  ##STR489##    (2-)COOCH.sub.2 CH.sub.2 Cl                                                                OCH.sub.3                                                                          OCH.sub.3                                                                           104                                   277                                                                                  ##STR490##    (2-)COOCH.sub.2 CH.sub.2 OCH.sub.3                                                         OCH.sub.3                                                                          OCH.sub.3                                                                           106                                   278                                                                                  ##STR491##    (2-)COOC.sub.3 H.sub.7 n                                                                   OCH.sub.3                                                                          OCH.sub.3                                                                           140                                   279                                                                                  ##STR492##    (2-)COOCH(CH.sub.3).sub.2                                                                  OCH.sub.3                                                                          OCH.sub.3                                                                           149                                   280                                                                                  ##STR493##    (2-)COOCH.sub.2 CH.sub.2 Cl                                                                OCH.sub.3                                                                          OCH.sub.3                                                                           117                                   281                                                                                  ##STR494##    (2-)COOCH.sub.2 CH.sub.2 OCH.sub.3                                                         OCH.sub.3                                                                          OCH.sub.3                                                                           116                                   282                                                                                  ##STR495##    (2-)COOC.sub.3 H.sub.7 n                                                                   CH.sub.3                                                                           OCH.sub.3                                                                           140                                   283                                                                                  ##STR496##    (2-)COOCH.sub.3                                                                            OCH.sub.3                                                                          OCH.sub.3                                                                           128                                   284                                                                                  ##STR497##    (2-)COOC.sub.2 H.sub.5                                                                     OCH.sub.3                                                                          OCH.sub.3                                                                           147                                   285                                                                                  ##STR498##    (2-)COOC.sub.3 H.sub.7 n                                                                   OCH.sub.3                                                                          OCH.sub.3                                                                           155                                   286                                                                                  ##STR499##    (2-)COOCH(CH.sub.3).sub.2                                                                  OCH.sub.3                                                                          OCH.sub.3                                                                           141                                   287                                                                                  ##STR500##    (2-)COOCH.sub.2 CH.sub.2 Cl                                                                OCH.sub.3                                                                          OCH.sub.3                                                                           118                                   288                                                                                  ##STR501##    (2-)COOCH.sub.3                                                                            CH.sub.3                                                                           OCH.sub.3                                                                           139                                   289                                                                                  ##STR502##    (2-)COOC.sub.2 H.sub.5                                                                     CH.sub.3                                                                           OCH.sub.3                                                                           158                                   290                                                                                  ##STR503##    (2-)COOC.sub.3 H.sub.7 n                                                                   CH.sub.3                                                                           OCH.sub.3                                                                           176                                   291                                                                                  ##STR504##    (2-)COOCH(CH.sub.3).sub.2                                                                  CH.sub.3                                                                           OCH.sub.3                                                                           149                                   292                                                                                  ##STR505##    (2-)COOCH.sub.2 CH.sub.2 Cl                                                                CH.sub.3                                                                           OCH.sub.3                                                                           130                                   293                                                                                  ##STR506##    (2-)COOCH.sub.2 CH.sub.2 OCH.sub.3                                                         CH.sub.3                                                                           OCH.sub.3                                                                           138                                   294                                                                                  ##STR507##    (2-)COOC.sub.2 H.sub.5                                                                     OCH.sub.3                                                                          OCH.sub.3                                                                           140                                   295                                                                                  ##STR508##    (2-)COOC.sub.3 H.sub.7 n                                                                   OCH.sub.3                                                                          OCH.sub.3                                                                           174                                   296                                                                                  ##STR509##    (2-)COOCH(CH.sub.3).sub.2                                                                  OCH.sub.3                                                                          OCH.sub.3                                                                           146                                   297                                                                                  ##STR510##    (2-)COOCH(CH.sub.3).sub.2                                                                  OCH.sub.3                                                                          OCH.sub.3                                                                           101                                   298                                                                                  ##STR511##    (2-)COOCH.sub.2 CH.sub.2 OCH.sub.3                                                         OCH.sub.3                                                                          OCH.sub.3                                                                            90                                   299                                                                                  ##STR512##    (2-)COOCH.sub.2 CH.sub.2 OCH.sub.3                                                         OCH.sub.3                                                                          OCH.sub.3                                                                            84                                   300                                                                                  ##STR513##    (2-)COOCH.sub.3                                                                            C.sub.2 H.sub.5                                                                    OCH.sub.3                                                                            93                                   301                                                                                  ##STR514##    (2-)COOC.sub.2 H.sub.5                                                                     C.sub.2 H.sub.5                                                                    OCH.sub.3                                                                           121                                   302                                                                                  ##STR515##    (2-)COOCH.sub.3                                                                            C.sub.2 H.sub.5                                                                    OCH.sub.3                                                                            86                                   303                                                                                  ##STR516##    (2-)COOC.sub.2 H.sub.5                                                                     C.sub.2 H.sub.5                                                                    OCH.sub.3                                                                            84                                   304                                                                                  ##STR517##    (2-)COOC.sub.2 H.sub.5                                                                     C.sub.2 H.sub.5                                                                    OCH.sub.3                                                                            78                                   305                                                                                  ##STR518##    (2-)COOCH.sub.3                                                                            C.sub.2 H.sub.5                                                                    OCH.sub.3                                                                            76                                   306                                                                                  ##STR519##    (2-)COOC.sub.2 H.sub.5                                                                     C.sub.2 H.sub.5                                                                    OCH.sub.3                                                                            81                                   307                                                                                  ##STR520##    (2-)COOC.sub.2 H.sub.5                                                                     CH.sub.3                                                                           OC.sub.2 H.sub.5                                                                     72                                   308                                                                                  ##STR521##    (2-)COOCH.sub.3                                                                            CH.sub.3                                                                           OC.sub.2 H.sub.5                                                                     76                                   309                                                                                  ##STR522##    (2-)COOC.sub.2 H.sub.5                                                                     C.sub.2 H.sub.5                                                                    OCH.sub.3                                                                            99                                   310                                                                                  ##STR523##    (2-)COOCH.sub.3                                                                            CH.sub.3                                                                           SCH.sub.3                                                                           118                                   311                                                                                  ##STR524##    (2-)COOC.sub.2 H.sub.5                                                                     CH.sub.3                                                                           SCH.sub.3                                                                           112                                   312                                                                                  ##STR525##    (2-)COOCH.sub.2 CH.sub.2 OCH.sub.3                                                         OCH.sub.3                                                                          OCH.sub.3                                                                            85                                   313                                                                                  ##STR526##    (2-)COOCH.sub.2 CH.sub.2 Cl                                                                OCH.sub.3                                                                          OCH.sub.3                                                                            76                                   314                                                                                  ##STR527##    (2-)COOCH.sub.2 CH.sub.2 OCH.sub.3                                                         OCH.sub.3                                                                          OCH.sub.3                                                                            80                                   315                                                                                  ##STR528##    (2-)COOCH.sub.2 CH.sub.2 OCH.sub.3                                                         CH.sub.3                                                                           OCH.sub.3                                                                            82                                   316                                                                                  ##STR529##    (2-)COOCH(CH.sub.3).sub.2                                                                  OCH.sub.3                                                                          OCH.sub.3                                                                            93                                   317                                                                                  ##STR530##    (2-)COOCH.sub.2 CH.sub.2 Cl                                                                OCH.sub.3                                                                          OCH.sub.3                                                                            87                                   318                                                                                  ##STR531##    (2-)COOCH.sub.2 CH.sub.2 OCH.sub.3                                                         OCH.sub.3                                                                          OCH.sub.3                                                                            94                                   319                                                                                  ##STR532##    (2-)COOCH.sub.2 CH.sub.2 OCH.sub.3                                                         CH.sub.3                                                                           OCH.sub.3                                                                            81                                   320                                                                                  ##STR533##    (2-)COOCH.sub.3                                                                            CH.sub.3                                                                           SCH.sub.3                                                                           109                                   321                                                                                  ##STR534##    (2-)COOCH.sub.3                                                                            OCH.sub.3                                                                          OCH.sub.3                                                                           187                                   322                                                                                  ##STR535##    (2-)COOCH.sub.3                                                                            OCH.sub.3                                                                          OCH.sub.3                                                                           160                                   323                                                                                  ##STR536##    (2-)COOCH.sub.3                                                                            CH.sub.3                                                                           OCH.sub.3                                                                           178                                   324                                                                                  ##STR537##    (2-)COOCH.sub.3                                                                            OCH.sub.3                                                                          OCH.sub.3                                                                           208                                   325                                                                                  ##STR538##    (2-)COOCH.sub.3                                                                            OCH.sub.3                                                                          OCH.sub.3                                                                           133                                   326                                                                                  ##STR539##    (2-)COOC.sub.2 H.sub.5                                                                     OCH.sub.3                                                                          OCH.sub.3                                                                           176                                   327                                                                                  ##STR540##    (2-)COOC.sub.3 H.sub.7 n                                                                   OCH.sub.3                                                                          OCH.sub.3                                                                           203                                   328                                                                                  ##STR541##    (2-)COOCH(CH.sub.3).sub.2                                                                  OCH.sub.3                                                                          OCH.sub.3                                                                           186                                   329                                                                                  ##STR542##    (2-)COOC.sub.4 H.sub.9 n                                                                   OCH.sub.3                                                                          OCH.sub.3                                                                           188                                   330                                                                                  ##STR543##    (2-)COOCH.sub.2 CH(CH.sub.3).sub.2                                                         OCH.sub.3                                                                          OCH.sub.3                                                                           172                                   331                                                                                  ##STR544##    (2-)COOCH.sub.3                                                                            CH.sub.3                                                                           OCH.sub.3                                  332                                                                                  ##STR545##    (2-)COOCH.sub.3                                                                            CH.sub.3                                                                           OCH.sub.3                                  333                                                                                  ##STR546##    (2-)COOC.sub.2 H.sub.5                                                                     CH.sub.3                                                                           OCH.sub.3                                  334                                                                                  ##STR547##    (2-)COOC.sub.2 H.sub.5                                                                     CH.sub.3                                                                           OCH.sub.3                                  335                                                                                  ##STR548##    (2-)COOCH.sub.3                                                                            OCH.sub.3                                                                          OCH.sub.3                                  336                                                                                  ##STR549##    (2-)COOCH.sub.3                                                                            OCH.sub.3                                                                          OCH.sub.3                                  337                                                                                  ##STR550##    (2-)COOC.sub.2 H.sub.5                                                                     OCH.sub.3                                                                          OCH.sub.3                                  338                                                                                  ##STR551##    (2-)COOC.sub.2 H.sub.5                                                                     OCH.sub.3                                                                          OCH.sub.3                                  339                                                                                  ##STR552##    (2-)COOCH.sub.3                                                                            CH.sub.3                                                                           OCH.sub.3                                  340                                                                                  ##STR553##    (2-)COOCH.sub.3                                                                            CH.sub.3                                                                           OCH.sub.3                                                                           178                                   341                                                                                  ##STR554##    (2-)COOCH.sub.3                                                                            CH.sub.3                                                                           OCH.sub.3                                  342                                                                                  ##STR555##    (2-)COOCH.sub.3                                                                            CH.sub.3                                                                           OCH.sub.3                                  343                                                                                  ##STR556##    (2-)COOCH.sub.3                                                                            OCH.sub.3                                                                          OCH.sub.3                                  344                                                                                  ##STR557##    (2-)COOCH.sub.3                                                                            OCH.sub.3                                                                          OCH.sub.3                                  345                                                                                  ##STR558##    (2-)COOCH.sub.3                                                                            CH.sub.3                                                                           OCH.sub.3                                  346                                                                                  ##STR559##    (2-)COOCH.sub.3                                                                            OCH.sub.3                                                                          OCH.sub.3                                  347                                                                                  ##STR560##    (2-)COOCH.sub.3                                                                            CH.sub.3                                                                           OCH.sub.3                                  348                                                                                  ##STR561##    (2-)COOCH.sub.3                                                                            OCH.sub.3                                                                          OCH.sub.3                                  349                                                                                  ##STR562##    (2-)COOCH.sub.3                                                                            CH.sub.3                                                                           OCH.sub.3                                  350                                                                                  ##STR563##    (2-)COOCH.sub.3                                                                            OCH.sub.3                                                                          OCH.sub.3                                  Example 351                                                                          ##STR564##                                                               __________________________________________________________________________

Process (b)

A mixture of 7.5 g (18.3 mmol) of N'-(4-methoxy-6-methyl-s-triazin-2-yl)-N"-amino-N"'-(2-ethoxycarbonylphenylsulphonyl)-guanidine, 2.28 g (20.3 mmol) of diazabicyclo-[2,2,2]-octane (DABCO) and 100 ml of methylene chloride is cooled to -70° C. and a solution of 4.53 g (18.3 mmol) of 2-ethoxycarbonylbenzenesulphonyl chloride in 20 ml of methylene chloride is added dropwise thereto with stirring. After removing the cooling bath the reaction mixture is stirred for a further 15 hours (finally at 20° C.). It is then diluted with 100 ml of methylene chloride and washed twice, each time with about 200 ml of water. The organic phase is dried with magnesium sulphate and filtered. The filtrate is freed from the solvent by distillation in a water-jet vacuum, and the residue is crystallised with ethyl acetate and the crystalline product is isolated by suction filtration.

6.3 g of first fraction of N'-(4-methoxy-6-methyl-s-triazin-2-yl)-N"-(2-ethoxycarbonylphenylsulphonylamino)-N"'-(2-ethoxycarbonylphenylsulphonyl)-guanidine are obtained. The mother liquor is concentrated by evaporation and the resulting residue is recrystallized with ethanol, whereupon a second product fraction (1.55 g) is obtained. Total yield: 7.85 g (69% of theory); melting point: 165° C.

USE EXAMPLES

The compound shown below is used as the comparison substance in the following use examples: ##STR565##

N'-(4,6-Dimethyl-pyrimidin-2-yl)-N"-acetamido-N"'-(2-chloro-phenylsulphonyl)-guanidine (known from EP-A 121,082).

The formulae of the compounds according to the invention used for the use examples are--with the numbering of the preparation examples ("Example No.")--shown individually below. ##STR566##

EXAMPLE A Pre-emergence test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.

Seeds of the test plants are sown in normal soil and, after 24 hours, watered with the preparation of the active compound. It is expedient to keep constant the amount of water per unit area. The concentration of the active compound in the preparation is of no importance, only the amount of active compound applied per unit area being decisive. After three weeks, the degree of damage to the plants is rated in % damage in comparison to the development of the untreated control. The figures denote:

0% =no action (like untreated control)

100%=total destruction

In this test, for example, the compounds according to the Preparation Examples (1), (3), (4), (5), (6), (7), (8), (9), (11), (21), (22), (23), (24), (25), (26), (27), (29) and (35) show considerably stronger action than the comparison substance (A).

EXAMPLE B Post-emergence test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.

Test plants which have a height of 5-15 cm are sprayed with the preparation of the active compound in such a way as to apply the particular amounts of active compound desired per unit area. The concentration of the spray liquor is so chosen that the particular amounts of active compound desired are applied in 2000 l of water/ha. After three weeks, the degree of damage to the plants is rated in % damage in comparison to the development of the untreated control. The figures denote:

0%=no action (like untreated control)

100%=total destruction

In this test, for example, the compounds according to the Preparation Examples (1), (3), (4), (5), (6), (7), (8), (9), (19), (11), (12), (13), (21), (22), (23), (24), (25), (26), (27), (29) and (35) show considerably stronger action than the comparison substance (A).

EXAMPLE C Test on transplanted paddy rice

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of benzyloxypolyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted to the desired concentration.

Plant receptacles (surface area 1/5000 are) are filled with soil from a paddy-field. Two rice plants (variety: Kinmaze) in the 2nd-3rd leaf stage (about 10 cm tall) are transplanted into the receptacles. Seeds of Echinochloa crus galli and/or Monochoria vaginal is and/or small rhizome sections of Eleocharis acicularis L. are sown in the moist earth. 2 days after transplanting the rice, the soil is covered with water to a depth of 3 cm. The active compound preparation is applied to the surface of the water. The concentration of the active compound in the preparation is of no importance, only the amount of active compound applied per unit area being decisive.

After applying the active compound, a vertically descending flow of water having a velocity of 2-3 cm per day is set up through the plant receptacle for 2 days. The test batches are then kept under overflowing conditions, where the water depth is 3 cm.

After 4 weeks, the degree of damage to the plants is evaluated in % damage (or weed action) in comparison to an untreated control.

The figures denote:

0%=no action (like the untreated control)

100%=total destruction

In this test, the good tolerability of the active compounds according to the invention--in particular of compounds (7) and (10)--in rice along with, at the same time, a very good weed action is apparent, whereas the very similar previously known compound (A) causes severe damage to the rice.

It will be appreciated that the instant specification and claims are set forth by way of illustration and not limitation, and that various modifications and changes may be made without departing from the spirit and scope of the present invention. 

What is claimed is:
 1. A sulphonylaminoguanidinoazine of the formula ##STR567## in which R¹ stands for the radical ##STR568## wherein R⁹ and R¹⁰ are identical or different and stand for hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, C₁ -C₆ -alkyl (which is optionally substituted by fluorine, chlorine, bromine, cyano, carboxyl, C₁ -C₄ -alkoxycarbonyl, C₁ -C₄ -alkylaminocarbonyl, di-(C₁ -C₄ -alkyl)-amino-carbonyl, hydroxyl, C₁ -C₄ -alkoxy, formyloxy, C₁ -C₄ -alkylcarbonyloxy, C₁ -C₄ -alkoxy-carbonyloxy, C₁ -C₄ -alkylamino-carbonyloxy, C₁ -C₄ -alkylthio, C₁ -C₄ -alkylsulphinyl, C₁ -C₄ -alkylsulphonyl, di-(C₁ -C₄ -alkyl)-aminosulphonyl, C₃ -C₆ -cycloalkyl or phenyl), for C₂ -C₆ -alkenyl (which is optionally substituted by fluorine, chlorine, bromine, cyano, C₁ -C₄ -alkoxy-carbonyl, carboxyl or phenyl), for C₂ -C₆ -alkinyl (which is optionally substituted by fluorine, chlorine, bromine, cyano, C₁ -C₄ -alkoxy-carbonyl, carboxyl or phenyl), for C₁ -C₄ -alkoxy (which is optionally substituted by fluorine, chlorine, bromine, cyano, carboxyl, C₁ -C₄ -alkoxy-carbonyl, C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio, C.sub. 1 -C₄ -alkylsulphinyl or C₁ -C₄ -alkylsulphonyl), for C₁ -C₄ -alkylthio (which is optionally substituted by fluorine, chlorine, bromine, cyano, carboxyl, C₁ -C₄ -alkoxy-carbonyl, C₁ -C₄ -alkylthio, C₁ -C₄ -alkylsulphinyl or C₁ -C₄ -alkylsulphonyl), for C₃ -C₆ -alkenyloxy (which is optionally substituted by fluorine, chlorine, bromine, cyano or C₁ -C₄ -alkoxycarbonyl), for C₂ -C₆ -alkenylthio (which is optionally substituted by fluorine, chlorine, bromine, cyano, nitro, C₁ -C₃ -alkylthio or C₁ -C₄ -alkoxycarbonyl), C₃ -C₆ -alkinyloxy, C₃ -C₆ -alkinylthio or for the radical --S(O)_(p) --R¹¹,wherein p stands for the numbers 1 or 2 and R¹¹ stands for C₁ -C₄ -alkyl (which is optionally substituted by fluorine, chlorine, bromine, cyano or C₁ -C₄ -alkoxy-carbonyl), C₃ -C₆ -alkenyl, C₃ -C₆ -alkinyl, C₁ -C₄ -alkoxy, C₁ -C₄ -alkoxy-C₁ -C₄ -alkylamino, C₁ -C₄ -alkylamino, di-(C₁ -C₄ -alkyl)-amino or for the radical --NHOR¹²,wherein R¹² stands for C₁ -C₁₂ -alkyl (which is optionally substituted by fluorine, chlorine, cyano, C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio, C₁ -C₄ -alkylsulphinyl, C₁ -C₄ -alkylsulphonyl, C₁ -C₄ -alkylcarbonyl, C₁ -C₄ -alkoxy-carbonyl, C₁ -C₄ -alkylamino-carbonyl or di-(C₁ -C₄ -alkyl)-amino-carbonyl), for C₃ -C₆ -alkenyl (which is optionally substituted by fluorine, chlorine or bromine), C₃ -C₆ -alkinyl, C₃ -C₆ -cycloalkyl, C₃ -C₆ -cycloalkyl-C₁ -C₂ -alkyl, phenyl-C₁ -C₂ -alkyl (which is optionally substituted by fluorine, chlorine, nitro, cyano, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy or C₁ -C₄ -alkoxycarbonyl), for benzylhydryl or for phenyl (which is optionally substituted by fluorine, chlorine, nitro, cyano, C₁ -C₄ -alkyl, trifluoromethyl, C₁ -C₄ -alkoxy, C₁ -C₂ -fluoroalkoxy, C₁ -C₄ -alkylthio, trifluoromethylthio or C₁ -C₄ -alkoxy-carbonyl), R⁹ and R¹⁰ furthermore stand for phenyl or phenoxy, for amino, C₁ -C₄ -alkylcarbonylamino, C₁ -C₄ -alkoxy-carbonylamino, C₁ -C₄ -alkylamino-carbonylamino, di-(C₁ -C₄ -alkyl)-amino-carbonylamino, or for the radical --CO--R¹³,wherein R¹³ stands for C₁ -C₆ -alkyl, C₁ -C₆ -alkoxy, C₃ -C₆ -cycloalkoxy, C₃ -C₆ -alkenyloxy, C₁ -C₄ -alkylthio, C₁ -C₄ -alkylamino, C₁ -C₄ -alkoxyamino, C₁ -C₄ -alkoxy-C₁ -C₄ -alkylamino or di-(C₁ -C₄ -alkyl)-amino (which are optionally substituted by fluorine and/or chlorine), R⁹ and R¹⁰ furthermore stand for C₁ -C₄ -alkylsulphonyloxy, di-(C₁ -C₄ -alkyl)-aminosulphonylamino, thiazolyloxy or for the radical --CH═N--R¹⁴,wherein R¹⁴ stands for C₁ -C₆ -alkyl which is optionally substituted by fluorine, chlorine, cyano, carboxyl, C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio, C₁ -C₄ -alkylsulphinyl or C₁ -C₄ -alkylsulphonyl, for benzyl which is optionally substituted by fluorine or chlorine, for C₃ -C₆ -alkenyl or C₃ -C₆ -alkinyl which are optionally substituted by fluorine or chlorine, for phenyl which is optionally substituted by fluorine, chlorine, bromine, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, trifluoromethyl, trifluoromethoxy or trifluoromethylthio, for C₁ -C₆ -alkoxy, C₃ -C₆ -alkenoxy, C₃ -C₆ -alkinoxy or benzyloxy which are optionally substituted by fluorine and/or chlorine, for amino, C₁ -C₄ -alkylamino, di-(C₁ -C₄ -alkyl)-amino, phenylamino, C₁ -C₄ -alkyl-carbonyl-amino, C₁ -C₄ -alkoxy-carbonylamino, C₁ -C₄ -alkyl-sulphonylamino or for phenylsulphonylamino which is optionally substituted by fluorine, chlorine, bromine or methyl,in addition, R¹ stands for the radical ##STR569## wherein R¹⁵ stands for hydrogen or C₁ -C₄ -alkyl, R¹⁶ and R¹⁷ are identical or different and stand for hydrogen, fluorine, chlorine, bromine, nitro, cyano, C₁ -C₄ -alkyl (which is optionally substituted by fluorine and/or chlorine), C₁ -C₄ -alkoxy (which is optionally substituted by fluorine and/or chlorine), carboxyl, C₁ -C₄ -alkoxy-carbonyl, C₁ -C₄ -alkylsulphonyl or di-(C₁ -C₄ -alkyl)-aminosulphonyl;in addition R¹ stands for the radical ##STR570## wherein R¹⁸ and R¹⁹ are identical or different and stand for hydrogen, fluorine, chlorine, bromine, nitro, cyano, C₁ -C₄ -alkyl (which is optionally substituted by fluorine and/or chlorine) or C₁ -C₄ alkoxy (which is optionally substituted by fluorine and/or chlorine);in addition R¹ stands for the radical ##STR571## wherein R²⁰ and R²¹ are identical or different and stand for hydrogen, fluorine, chlorine, bromine, nitro, cyano, C₁ -C₄ -alkyl (which is optionally substituted by fluorine and/or chlorine), C₁ -C₄ -alkoxy (which is optionally substituted by fluorine and/or chlorine), for C₁ -C₄ -alkylthio, C₁ -C₄ -alkylsulphinyl or C₁ -C₄ -alkylsulphonyl (which are optionally substituted by fluorine and/or chlorine) and also for di-(C₁ -C₄ -alkyl)-aminosulphonyl or C₁ -C₄ -alkoxy-carbonyl;in addition R¹ stands for the radical ##STR572## wherein R²² and R²³ are identical or different and stand for hydrogen, fluorine, chlorine, bromine, C₁ -C₄ -alkyl (which is optionally substituted by fluorine and/or bromine), C₁ -C₄ -alkoxy (which is optionally substituted by fluorine and/or chlorine), for C₁ -C₄ -alkylthio, C₁ -C₄ -alkylsulphinyl or C₁ -C₄ -alkylsulphonyl (which are optionally substituted by fluorine and/or chlorine), or for di-(C₁ -C₄ -alkyl)-aminosulphonyl;in addition R¹ stands for the radical ##STR573## wherein R²⁴ and R²⁵ are identical or different and stand for hydrogen, fluorine, chlorine, bromine, cyano, nitro, C₁ -C₄ -alkyl (which is optionally substituted by fluorine and/or chlorine), C₁ -C₄ -alkoxy (which is optionally substituted by fluorine and/or chlorine), C₁ -C₄ -alkylthio, C₁ -C₄ -alkylsulphinyl or C₁ -C₄ -alkylsulphonyl (which is optionally substituted by fluorine and/or chlorine), di-(C₁ -C₄ -alkyl)-amino-sulphonyl or C₁ -C₄ -alkoxy-carbonyl, and A satnds for oxygen, sulphur or the grouping N--Z¹,wherein Z¹ stands for hydrogen, C₁ -C₄ -alkyl (which is optionally substituted by fluorine, chlorine, bromine or cyano), C₃ -C₆ -cycloalkyl, benzyl, phenyl (which is optionally substituted by fluorine, chlorine, bromine or nitro), C₁ -C₄ -alkylcarbonyl, C₁ -C₄ -alkoxy-carbonyl or di-(C₁ -C₄ -alkyl)-aminocarbonyl;in addition R¹ stands for the radical ##STR574## wherein R²⁶ stands for hydrogen, C₁ -C₅ -alkyl or halogen, R²⁷ satnds for hydrogen or C₁ -C₅ -alkyl and Y¹ stands for sulphur or the grouping N--R²⁸,wherein R²⁸ stands for hydrogen or C₁ -C₅ -alkyl,in addition R¹ stands for the radical ##STR575## wherein R²⁹ stands for hydrogen, C₁ -C₄ -alkyl or phenyl, R³⁰ stands for hydrogen, halogen, cyano, nitro, C₁ -C₄ -alkyl (which is optionally substituted by fluorine and/or chlorine), C₁ -C₄ -alkoxy (which is optionally substituted by fluorine and/or chlorine) or C₁ -C₄ -alkoxy-carbonyl and R³¹ stands for hydrogen, halogen or C₁ -C₄ -alkyl,in addition, R¹ stands for the radical ##STR576## wherein R³² stands for C₁ -C₃ -alkyl and R³³ stands for C₁ -C₄ -alkyl,in addition R¹ stands for the radical ##STR577## in addition R² has the meaning given above for R¹, but does not have to be identical with R¹ in each individual case, and in addition can stand for di-(C₁ -C₃ -alkyl)-amino or for C₁ -C₈ -alkyl which is optionally substituted by halogen, provided, however, that R² cannot be unsubstituted phenyl or fluorine-, chlorine-, bromine-or methyl-substituted phenyl,in addition R³ stands for hydrogen, fluorine, chlorine, bromine, C₁ -C₄ -alkyl, C₁ -C₄ -halogenoalkyl, C₁ -C₂ -alkoxy-C₁ -C₂ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -halogenoalkoxy, C₁ -C₄ -alkylthio, C₁ -C₄ -halogenoalkylthio, amino, C₁ -C₄ -alkylamino, dimethylamino or diethylamino, R⁵ stands for hydrogen, fluorine, chlorine, bromine, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -halogenoalkoxy, C₁ -C₄ -alkylthio, C₁ -C₄ -alkylamino, dimethylamino or diethylamino, and M stands for hydrogen or a sodium equivalent, a potassium equivalent or a calcium equivalent, an ammonium equivalent, a C₁ -C₆ -alkylammonium equivalent, a di-(C₁ -C₄ -alkyl)-ammonium or a tri-(C₁ -C₄ -alkyl)-ammonium equivalent.
 2. A sulphonylaminoguanidinoazine according to claim 1,in which R¹ stands for the radical ##STR578## wherein R⁹ stands for fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy, difluoromethoxy, trifluoromethoxy, C₁ -C₃ -alkylthio, C₁ -C₃ -alkylsulphinyl, C₁ -C₃ -alkylsulphonyl, dimethylaminosulphonyl, diethylaminosulphonyl, N-methoxy-N-methylaminosulphonyl, phenyl, phenoxy or C₁ -C₃ -alkoxy-carbonyl and R¹⁰ stands for hydrogen;in addition R¹ stands for the radical ##STR579## wherein R¹⁵ satnds for hydrogen, R¹⁶ stands for fluorine, chlorine, bromine, methyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, methoxycarbonyl, ethoxycarbonyl, methylsulphonyl or dimethylaminosulphonyl and R¹⁷ stands for hydrogen;in addition R¹ stands for the radical ##STR580## wherein R stands for C₁ -C₂ -alkyl, or R¹ stands for the radical ##STR581## wherein R stands for C₁ -C₂ -alkyl;in addition R² stands for C₁ -C₄ -alkyl which is optionally substituted by fluorine or chlorine or for substituted phenyl which is substituted by ethyl-, propyl-, trifluoromethyl chlorodifluoromethyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, amino, acetamido, methoxycarbonyl and/or ethoxycarbonyl, R³ stands for hydrogen, fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, methylthio, ethylthio, amino, methylamino, ethylamino, dimethylamino or diethylamino, R⁵ stands for hydrogen, fluorine, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, propoxy, isopropoxy, difluoromethoxy, methylthio, ethylthio, methylamino, ethylamino, dimethylamino or diethylamino, and M stands for hydrogen or a sodium equivalent, potassium equivalent or calcium equivalent, an ammonium equivalent or a C₁ -C₄ -alkyl-ammonium equivalent.
 3. A compound according to claim 1, wherein such compound is N'-(4-methoxy-6-methyl-s-triazin-2-yl)-N"-(2-methoxycarbonyl-phenylsulphonylamino)-N'"-(2-ethoxycarbonyl-phenylsulphonyl)-guanidine.
 4. A compound according to claim 1, wherein such compound is N'-(4,6-dimethoxy-s-triazin-2-yl)-N"-(2-methoxycarbonyl-phenylsulphonylamino)-N'"-(2-methoxycarbonyl-phenylsulphonyl)-guanidine.
 5. A compound according to claim 1, wherein such compound is N'-(4-methoxy-6-methyl-s-triazin-2-yl)-N"-[2-(2-methoxyethoxy)-carbonyl-phenylsulphonylamino]-N'"-(2-ethoxycarbonyl-phenylsulphonyl)-guanidine.
 6. A compound according to claim 1, wherein such compound is N'-(4-methoxy-6-methyl-s-triazin-2-yl)-N"-(2-methoxycarbonyl-phenylsulphonylamino)-N'"-(2-n-propoxycarbonyl-phenylsulphonyl)-guanidine.
 7. A compound according to claim 1, wherein such compound is N'-(4-methoxy-6-methyl-s-triazin-2-yl)-N"-(2-n-propoxycarbonyl-phenylsulphonylamino)-N'"-(2-n-propoxycarbonyl-phenylsulphonyl)-guanidine.
 8. A compound according to claim 1, wherein such compound is N'-(4-methoxy-6-methyl-s-triazin-2-yl)-N"-(2-methoxycarbonyl-phenylsulphonylamino)-N'"-(2-isopropoxycarbonyl-phenylsulphonyl)-guanidine.
 9. A compound according to claim 1, wherein such compound is N'-(4-methoxy-6-methyl-s-triazin-2-yl)-N"-(2-ethoxycarbonyl-phenylsulphonylamino)-N'"-(2-ethoxycarbonyl-phenylsulphonyl)-guanidine.
 10. A herbicidal composition comprising a herbicidally effective amount of a compound according to claim 1 and a diluent.
 11. A method of combating unwanted vegetation which comprises applying to such vegetation or to a habitat from which it is desired to exclude such vegetation a herbicidally effective amount of a compound according to claim
 1. 12. A method of combating unwanted vegetation which comprises applying to such vegetation or to a habitat from which it is desired to exclude such vegetation a herbicidally effective amount of a compound selected from the group consisting ofN'-(4-methoxy-6-methyl-s-triazin-2-yl)-N"-(2-methoxycarbonyl-phenylsulphonylamino)-N'"-(2-ethoxy-carbonyl-phenylsulphonyl)-guanidine, N'-(4,6-dimethoxy-s-triazin-2-yl)-N"-(2-methoxycarbonyl-phenylsulphonylamino)-N'"-(2-methoxy-carbonyl-phenylsulphonyl)-guanidine, N'-(4-methoxy-6-methyl-s-triazin-2-yl)-N"-[2-(2-methoxyethoxy)-carbonyl-phenylsulphonylamino]-N'"-(2-ethoxycarbonyl-phenylsulphonyl)-guanidine, N'-(4-methoxy-6-methyl-s-triazin-2-yl)-N"-(2-methoxycarbonyl-phenylsulphonylamino)-N'"-(2-n-propoxy-carbonyl-phenylsulphonyl)-guanidine, N'-(4-methoxy-6-methyl-s-triazin-2-yl)-N"-(2-n-propoxycarbonyl-phenylsulphonylamino)-N'"-(2-n-propoxycarbonyl-phenylsulphonyl)-guanidine, N'-(4-methoxy-6-methyl-s-triazin-2-yl)-N"-(2-methoxycarbonyl-phenylsulphonylamino)-N'"-(2-isopropoxy-carbonyl-phenylsulphonyl)-guanidine and N'-(4-methoxy-6-methyl-s-triazin-2-yl)-N"-(2-ethoxycarbonyl-phenylsulphonylamino)-N'"-(2-ethoxy-carbonyl-phenylsulphonyl)-guanidine. 